61228-92-0

Basic information

• Product Name: PERIPLANONEB
• Synonyms: PERIPLANONEB;(1R,2R,5S,6E,10R)-8-Methylene-5-(1-methylethyl)spiro[11-oxabicyclo[8.1.0]undec-6-ene-2,2'-oxiran]-3-one;(1Z,5E)-1,10(14)-Diepoxy-4(15),5-germacradien-9-one
• CAS NO: 61228-92-0
• Molecular Formula: C₁₅H₂₀O₃
• Molecular Weight: 248.32
• Mol File: 61228-92-0.mol
• Article Data: 6

Chemical Properties

• Melting Point: 47-50°
• Appearance: /
• CAS DataBase Reference: PERIPLANONEB(CAS DataBase Reference)
• NIST Chemistry Reference: PERIPLANONEB(61228-92-0)
• EPA Substance Registry System: PERIPLANONEB(61228-92-0)

Safety Data

• Hazardous Substances Data: 61228-92-0(Hazardous Substances Data)

Usage

General Description

Periplanone B is a naturally occurring pheromone derived from the American cockroach. It serves as a powerful sex attractant in the species and has significant potential in pest control applications, where it could be used to lure cockroaches into traps or poison baits. Periplanone B has a complex chemical structure, classified as a macrocyclic ketone, and is difficult to synthesize in the laboratory due to the presence of several chiral centers. Its possible applications in household and commercial pest control products have prompted extensive research and efforts to develop efficient methods for its synthesis.

Synthetic route

(1S,3S,4E,8R,9R,10S)-8,9-epoxy-10,10-epoxymethano-3-isopropyl-6-methylene-4-cyclodecen-1-ol (70800-65-6, 70831-70-8, 70831-72-0, 70831-75-3, 84236-08-8) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
With dipyridinium dichromate In N,N-dimethyl-formamide for 2h; Ambient temperature;	92%
With dipyridinium dichromate In N,N-dimethyl-formamide	92%
With 3 A molecular sieve; pyridinium chlorochromate In dichloromethane for 1h; Ambient temperature;	88%

methylenedimethyl sulfurane (6814-64-8, 40651-06-7) + (E)-(1R,5S,10R)-5-Isopropyl-8-methylene-11-oxa-bicyclo[8.1.0]undec-6-ene-2,3-dione (105930-41-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
In tetrahydrofuran; dimethyl sulfoxide at 0℃; for 0.166667h;

(4S,5E,9R,10R)-9,10-epoxy-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one (105930-39-0) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 2: imidazole / dimethylformamide 3: n-BuLi / tetrahydrofuran 4: n-Bu4NF / tetrahydrofuran 5: 92 percent / PDC / dimethylformamide View Scheme
Multi-step reaction with 5 steps 1: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 2: dimethylformamide / 16 h / 40 °C 3: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 4: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 5: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: 1) LiN(TMS)2, 2) MoO5*HMPA*Py / 1) THF, 30 min, 2) -70 degC, 5 min 2: PCC / CH2Cl2 / 5 h / Ambient temperature; Molecular sieves 3A 3: tetrahydrofuran; dimethylsulfoxide / 0.17 h / 0 °C View Scheme
Multi-step reaction with 5 steps 1: 1) LiN(TMS)2, 2) MoO5*HMPA*py / 1) -78 deg C, 1 h, THF, 2) -20 deg C, 25 min 2: imidazole / dimethylformamide / 17 h / Ambient temperature 3: 1) n-BuLi / 1) THF, hexane, 10 min, 2a) THF, -15 deg C, 10 min, 2b) 20 min, 0 deg C 4: (n-Bu)4NF / tetrahydrofuran / 0.17 h / Ambient temperature 5: 92 percent / PDC / dimethylformamide / 2 h / Ambient temperature View Scheme

(2S,4S,5E,9R,10R)-2-t-butyldimethylsilyloxy-9,10-epoxy-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one (113666-35-6) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: n-BuLi / tetrahydrofuran 2: n-Bu4NF / tetrahydrofuran 3: 92 percent / PDC / dimethylformamide View Scheme
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 2: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 3: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: 1) n-BuLi / 1) THF, hexane, 10 min, 2a) THF, -15 deg C, 10 min, 2b) 20 min, 0 deg C 2: (n-Bu)4NF / tetrahydrofuran / 0.17 h / Ambient temperature 3: 92 percent / PDC / dimethylformamide / 2 h / Ambient temperature View Scheme

(1S,3S,4E,8R,9R,10R)-1-t-butyldimethylsilyloxy-8,9-epoxy-6-methylene-10,10-methylenoxy-3-(1-methylethyl)-4-cyclodecene (70552-76-0, 70614-01-6, 113666-36-7) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: n-Bu4NF / tetrahydrofuran 2: 92 percent / PDC / dimethylformamide View Scheme
Multi-step reaction with 2 steps 1: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 2: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1: (n-Bu)4NF / tetrahydrofuran / 0.17 h / Ambient temperature 2: 92 percent / PDC / dimethylformamide / 2 h / Ambient temperature View Scheme

(4S,5E,7S,9R,10R)-9,10-epoxy-7-hydroxymethyl-4-isopropyl-5-cyclodecen-1-one (123536-67-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 7 steps 1: 99 percent / n-Bu3P / tetrahydrofuran 2: 90 percent / H2O2 / tetrahydrofuran 3: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 4: imidazole / dimethylformamide 5: n-BuLi / tetrahydrofuran 6: n-Bu4NF / tetrahydrofuran 7: 92 percent / PDC / dimethylformamide View Scheme
Multi-step reaction with 7 steps 1: 99 percent / (n-Bu)3P / tetrahydrofuran / 0.83 h / Ambient temperature 2: 90 percent / 35percent H2O2 / tetrahydrofuran / 13 h / Ambient temperature 3: 1) LiN(TMS)2, 2) MoO5*HMPA*py / 1) -78 deg C, 1 h, THF, 2) -20 deg C, 25 min 4: imidazole / dimethylformamide / 17 h / Ambient temperature 5: 1) n-BuLi / 1) THF, hexane, 10 min, 2a) THF, -15 deg C, 10 min, 2b) 20 min, 0 deg C 6: (n-Bu)4NF / tetrahydrofuran / 0.17 h / Ambient temperature 7: 92 percent / PDC / dimethylformamide / 2 h / Ambient temperature View Scheme

(2S,4S,5E,9R,10R)-9,10-epoxy-2-hydroxy-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one (113666-34-5) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: imidazole / dimethylformamide 2: n-BuLi / tetrahydrofuran 3: n-Bu4NF / tetrahydrofuran 4: 92 percent / PDC / dimethylformamide View Scheme
Multi-step reaction with 4 steps 1: dimethylformamide / 16 h / 40 °C 2: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 3: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 4: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 4 steps 1: imidazole / dimethylformamide / 17 h / Ambient temperature 2: 1) n-BuLi / 1) THF, hexane, 10 min, 2a) THF, -15 deg C, 10 min, 2b) 20 min, 0 deg C 3: (n-Bu)4NF / tetrahydrofuran / 0.17 h / Ambient temperature 4: 92 percent / PDC / dimethylformamide / 2 h / Ambient temperature View Scheme

(1S,5S,6R)-5-(2-Ethoxy-ethoxymethyl)-6-((Z)-3-methyl-but-1-enyl)-1-vinyl-cyclohex-2-enol → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 10 steps 1: 74 percent / KH, 18-crown-6 / 1,2-dimethoxy-ethane 2: KH, t-BuOOH / tetrahydrofuran 3: PPTS / ethanol 4: 99 percent / n-Bu3P / tetrahydrofuran 5: 90 percent / H2O2 / tetrahydrofuran 6: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 7: imidazole / dimethylformamide 8: n-BuLi / tetrahydrofuran 9: n-Bu4NF / tetrahydrofuran 10: 92 percent / PDC / dimethylformamide View Scheme

(2Z,6E)-(5S,8S)-5-(2-Ethoxy-ethoxymethyl)-8-isopropyl-cyclodeca-2,6-dienone → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: KH, t-BuOOH / tetrahydrofuran 2: PPTS / ethanol 3: 99 percent / n-Bu3P / tetrahydrofuran 4: 90 percent / H2O2 / tetrahydrofuran 5: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 6: imidazole / dimethylformamide 7: n-BuLi / tetrahydrofuran 8: n-Bu4NF / tetrahydrofuran 9: 92 percent / PDC / dimethylformamide View Scheme

(E)-(1R,5S,8S,10R)-8-(2-Ethoxy-ethoxymethyl)-5-isopropyl-11-oxa-bicyclo[8.1.0]undec-6-en-2-one → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 8 steps 1: PPTS / ethanol 2: 99 percent / n-Bu3P / tetrahydrofuran 3: 90 percent / H2O2 / tetrahydrofuran 4: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 5: imidazole / dimethylformamide 6: n-BuLi / tetrahydrofuran 7: n-Bu4NF / tetrahydrofuran 8: 92 percent / PDC / dimethylformamide View Scheme

(E)-(1R,5S,8S,10R)-5-Isopropyl-8-phenylselanylmethyl-11-oxa-bicyclo[8.1.0]undec-6-en-2-one (123453-99-6) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 90 percent / H2O2 / tetrahydrofuran 2: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 3: imidazole / dimethylformamide 4: n-BuLi / tetrahydrofuran 5: n-Bu4NF / tetrahydrofuran 6: 92 percent / PDC / dimethylformamide View Scheme

(5S,6R)-5-(2-Ethoxy-ethoxymethyl)-6-((Z)-3-methyl-but-1-enyl)-cyclohex-2-enone → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 11 steps 1: 86 percent / diethyl ether 2: 74 percent / KH, 18-crown-6 / 1,2-dimethoxy-ethane 3: KH, t-BuOOH / tetrahydrofuran 4: PPTS / ethanol 5: 99 percent / n-Bu3P / tetrahydrofuran 6: 90 percent / H2O2 / tetrahydrofuran 7: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 8: imidazole / dimethylformamide 9: n-BuLi / tetrahydrofuran 10: n-Bu4NF / tetrahydrofuran 11: 92 percent / PDC / dimethylformamide View Scheme

(5S,6S)-5-(2-Ethoxy-ethoxymethyl)-6-((1S,2S)-1-hydroxy-3-methyl-2-phenylselanyl-butyl)-cyclohex-2-enone → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 12 steps 1: MsCl, Et3N / CH2Cl2 2: 86 percent / diethyl ether 3: 74 percent / KH, 18-crown-6 / 1,2-dimethoxy-ethane 4: KH, t-BuOOH / tetrahydrofuran 5: PPTS / ethanol 6: 99 percent / n-Bu3P / tetrahydrofuran 7: 90 percent / H2O2 / tetrahydrofuran 8: 86 percent / LiN(TMS)2, MoO5*HMPA*Py / tetrahydrofuran 9: imidazole / dimethylformamide 10: n-BuLi / tetrahydrofuran 11: n-Bu4NF / tetrahydrofuran 12: 92 percent / PDC / dimethylformamide View Scheme

(4S,5E)-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one (105930-38-9) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 2: NaIO4 / methanol; H2O / 22 h 3: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 4: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 5: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 6: dimethylformamide / 16 h / 40 °C 7: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 8: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 9: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 5 steps 2: tBuOOH 3: 1) LiN(TMS)2, 2) MoO5*HMPA*Py / 1) THF, 30 min, 2) -70 degC, 5 min 4: PCC / CH2Cl2 / 5 h / Ambient temperature; Molecular sieves 3A 5: tetrahydrofuran; dimethylsulfoxide / 0.17 h / 0 °C View Scheme

(R)-3-(1-methylethyl)-6-oxoheptanal dimethylacetal (105897-85-6) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 26 steps 1: 1.) NaH / 1.) dioxane, MeOH, reflux; 2.) reflux, 90 min 2: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 3: LiAlH4 / diethyl ether / 1 h / below 10 deg C 4: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 5: OsO4, NaIO4 / diethyl ether; H2O / 7 h 6: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 7: pyridine / Ambient temperature 8: 75 percent AcOH / 1 h / 30 °C 9: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 10: NaOAc / 0.67 h / 130 °C 11: 1 percent NaOMe / methanol / 1 h / Ambient temperature 12: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 13: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 14: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 15: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 16: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 17: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 18: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 19: NaIO4 / methanol; H2O / 22 h 20: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 21: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 22: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 23: dimethylformamide / 16 h / 40 °C 24: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 25: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 26: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 27 steps 1: 1.) NaH / 1.) dioxane, MeOH, reflux; 2.) reflux, 90 min 2: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 3: LiAlH4 / diethyl ether / 1 h / below 10 deg C 4: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 5: OsO4, NaIO4 / diethyl ether; H2O / 7 h 6: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 7: pyridine / Ambient temperature 8: 75 percent AcOH / 1 h / 30 °C 9: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 10: NaOAc / 0.67 h / 130 °C 11: 1 percent NaOMe / methanol / 1 h / Ambient temperature 12: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 13: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 14: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 15: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 16: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 17: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 18: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 19: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 20: NaIO4 / methanol; H2O / 22 h 21: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 22: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 23: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 24: dimethylformamide / 16 h / 40 °C 25: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 26: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 27: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 26 steps 1: 1.) NaH / 1.) dioxane, MeOH, reflux; 2.) reflux, 90 min 2: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 3: LiAlH4 / diethyl ether / 1 h / below 10 deg C 4: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 5: OsO4, NaIO4 / diethyl ether; H2O / 7 h 6: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 7: pyridine / Ambient temperature 8: 75 percent AcOH / 1 h / 30 °C 9: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 10: NaOAc, Ac2O / 0.67 h / 130 °C 11: 1 percent NaOMe / methanol / 1 h / Ambient temperature 12: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 13: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 14: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 15: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 16: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 17: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 18: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 19: NaIO4 / methanol; H2O / 22 h 20: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 21: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 22: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 23: dimethylformamide / 16 h / 40 °C 24: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 25: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 26: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 27 steps 1: 1.) NaH / 1.) dioxane, MeOH, reflux; 2.) reflux, 90 min 2: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 3: LiAlH4 / diethyl ether / 1 h / below 10 deg C 4: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 5: OsO4, NaIO4 / diethyl ether; H2O / 7 h 6: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 7: pyridine / Ambient temperature 8: 75 percent AcOH / 1 h / 30 °C 9: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 10: NaOAc, Ac2O / 0.67 h / 130 °C 11: 1 percent NaOMe / methanol / 1 h / Ambient temperature 12: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 13: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 14: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 15: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 16: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 17: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 18: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 19: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 20: NaIO4 / methanol; H2O / 22 h 21: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 22: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 23: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 24: dimethylformamide / 16 h / 40 °C 25: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 26: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 27: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(R)-3-(1-methylethyl)-6-oxo-9-decenal dimethylacetal (105897-86-7) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 24 steps 1: LiAlH4 / diethyl ether / 1 h / below 10 deg C 2: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 3: OsO4, NaIO4 / diethyl ether; H2O / 7 h 4: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 5: pyridine / Ambient temperature 6: 75 percent AcOH / 1 h / 30 °C 7: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 8: NaOAc / 0.67 h / 130 °C 9: 1 percent NaOMe / methanol / 1 h / Ambient temperature 10: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 11: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 12: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 13: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 14: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 15: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 16: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 17: NaIO4 / methanol; H2O / 22 h 18: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 19: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 20: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 21: dimethylformamide / 16 h / 40 °C 22: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 23: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 24: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 25 steps 1: LiAlH4 / diethyl ether / 1 h / below 10 deg C 2: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 3: OsO4, NaIO4 / diethyl ether; H2O / 7 h 4: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 5: pyridine / Ambient temperature 6: 75 percent AcOH / 1 h / 30 °C 7: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 8: NaOAc / 0.67 h / 130 °C 9: 1 percent NaOMe / methanol / 1 h / Ambient temperature 10: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 11: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 12: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 13: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 14: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 15: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 16: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 17: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 18: NaIO4 / methanol; H2O / 22 h 19: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 20: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 21: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 22: dimethylformamide / 16 h / 40 °C 23: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 24: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 25: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 24 steps 1: LiAlH4 / diethyl ether / 1 h / below 10 deg C 2: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 3: OsO4, NaIO4 / diethyl ether; H2O / 7 h 4: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 5: pyridine / Ambient temperature 6: 75 percent AcOH / 1 h / 30 °C 7: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 8: NaOAc, Ac2O / 0.67 h / 130 °C 9: 1 percent NaOMe / methanol / 1 h / Ambient temperature 10: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 11: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 12: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 13: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 14: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 15: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 16: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 17: NaIO4 / methanol; H2O / 22 h 18: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 19: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 20: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 21: dimethylformamide / 16 h / 40 °C 22: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 23: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 24: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 25 steps 1: LiAlH4 / diethyl ether / 1 h / below 10 deg C 2: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 3: OsO4, NaIO4 / diethyl ether; H2O / 7 h 4: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 5: pyridine / Ambient temperature 6: 75 percent AcOH / 1 h / 30 °C 7: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 8: NaOAc, Ac2O / 0.67 h / 130 °C 9: 1 percent NaOMe / methanol / 1 h / Ambient temperature 10: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 11: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 12: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 13: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 14: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 15: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 16: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 17: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 18: NaIO4 / methanol; H2O / 22 h 19: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 20: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 21: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 22: dimethylformamide / 16 h / 40 °C 23: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 24: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 25: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(1RS,4S,5E)-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-ol (105897-92-5, 113666-31-2, 113666-38-9) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 10 steps 1: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 2: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 3: NaIO4 / methanol; H2O / 22 h 4: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 5: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 6: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 7: dimethylformamide / 16 h / 40 °C 8: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 9: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 10: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 6 steps 1: 72 percent / PCC-NaOH / CH2Cl2 3: tBuOOH 4: 1) LiN(TMS)2, 2) MoO5*HMPA*Py / 1) THF, 30 min, 2) -70 degC, 5 min 5: PCC / CH2Cl2 / 5 h / Ambient temperature; Molecular sieves 3A 6: tetrahydrofuran; dimethylsulfoxide / 0.17 h / 0 °C View Scheme

(1RS,2E,4S,7RS)-7-hydroxy-4-(1-methylethyl)-1-phenylthio-2-cyclodecene-1-methyl benzoate (105897-91-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 11 steps 1: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 2: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 3: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 4: NaIO4 / methanol; H2O / 22 h 5: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 6: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 7: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 8: dimethylformamide / 16 h / 40 °C 9: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 10: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 11: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 7 steps 1: 82 percent / sodium naphthalenide / tetrahydrofuran / 0.08 h / -78 °C 2: 72 percent / PCC-NaOH / CH2Cl2 4: tBuOOH 5: 1) LiN(TMS)2, 2) MoO5*HMPA*Py / 1) THF, 30 min, 2) -70 degC, 5 min 6: PCC / CH2Cl2 / 5 h / Ambient temperature; Molecular sieves 3A 7: tetrahydrofuran; dimethylsulfoxide / 0.17 h / 0 °C View Scheme

(2Z,6E,8S)-5-methylene-8-(1-methylethyl)-2,6-cyclodecadien-1-one (113666-33-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 2: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 3: dimethylformamide / 16 h / 40 °C 4: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 5: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 6: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 4 steps 1: tBuOOH 2: 1) LiN(TMS)2, 2) MoO5*HMPA*Py / 1) THF, 30 min, 2) -70 degC, 5 min 3: PCC / CH2Cl2 / 5 h / Ambient temperature; Molecular sieves 3A 4: tetrahydrofuran; dimethylsulfoxide / 0.17 h / 0 °C View Scheme

(R)-8-(2,2-Dimethoxy-ethyl)-9-methyl-dec-1-en-5-ol (113590-01-5) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 23 steps 1: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 2: OsO4, NaIO4 / diethyl ether; H2O / 7 h 3: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 4: pyridine / Ambient temperature 5: 75 percent AcOH / 1 h / 30 °C 6: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 7: NaOAc / 0.67 h / 130 °C 8: 1 percent NaOMe / methanol / 1 h / Ambient temperature 9: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 10: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 11: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 12: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 13: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 14: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 15: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 16: NaIO4 / methanol; H2O / 22 h 17: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 18: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 19: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 20: dimethylformamide / 16 h / 40 °C 21: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 22: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 23: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 24 steps 1: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 2: OsO4, NaIO4 / diethyl ether; H2O / 7 h 3: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 4: pyridine / Ambient temperature 5: 75 percent AcOH / 1 h / 30 °C 6: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 7: NaOAc / 0.67 h / 130 °C 8: 1 percent NaOMe / methanol / 1 h / Ambient temperature 9: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 10: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 11: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 12: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 13: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 14: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 15: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 16: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 17: NaIO4 / methanol; H2O / 22 h 18: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 19: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 20: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 21: dimethylformamide / 16 h / 40 °C 22: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 23: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 24: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 23 steps 1: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 2: OsO4, NaIO4 / diethyl ether; H2O / 7 h 3: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 4: pyridine / Ambient temperature 5: 75 percent AcOH / 1 h / 30 °C 6: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 7: NaOAc, Ac2O / 0.67 h / 130 °C 8: 1 percent NaOMe / methanol / 1 h / Ambient temperature 9: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 10: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 11: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 12: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 13: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 14: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 15: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 16: NaIO4 / methanol; H2O / 22 h 17: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 18: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 19: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 20: dimethylformamide / 16 h / 40 °C 21: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 22: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 23: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 24 steps 1: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 2: OsO4, NaIO4 / diethyl ether; H2O / 7 h 3: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 4: pyridine / Ambient temperature 5: 75 percent AcOH / 1 h / 30 °C 6: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 7: NaOAc, Ac2O / 0.67 h / 130 °C 8: 1 percent NaOMe / methanol / 1 h / Ambient temperature 9: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 10: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 11: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 12: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 13: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 14: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 15: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 16: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 17: NaIO4 / methanol; H2O / 22 h 18: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 19: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 20: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 21: dimethylformamide / 16 h / 40 °C 22: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 23: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 24: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(R)-7-(2,2-Dimethoxy-ethyl)-4-(2-methoxy-ethoxymethoxy)-8-methyl-nonan-1-ol (113590-03-7) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 20 steps 1: pyridine / Ambient temperature 2: 75 percent AcOH / 1 h / 30 °C 3: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 4: NaOAc / 0.67 h / 130 °C 5: 1 percent NaOMe / methanol / 1 h / Ambient temperature 6: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 7: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 8: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 9: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 10: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 11: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 12: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 13: NaIO4 / methanol; H2O / 22 h 14: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 15: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 16: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 17: dimethylformamide / 16 h / 40 °C 18: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 19: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 20: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 21 steps 1: pyridine / Ambient temperature 2: 75 percent AcOH / 1 h / 30 °C 3: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 4: NaOAc / 0.67 h / 130 °C 5: 1 percent NaOMe / methanol / 1 h / Ambient temperature 6: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 7: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 8: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 9: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 10: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 11: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 12: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 13: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 14: NaIO4 / methanol; H2O / 22 h 15: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 16: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 17: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 18: dimethylformamide / 16 h / 40 °C 19: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 20: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 21: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 20 steps 1: pyridine / Ambient temperature 2: 75 percent AcOH / 1 h / 30 °C 3: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 4: NaOAc, Ac2O / 0.67 h / 130 °C 5: 1 percent NaOMe / methanol / 1 h / Ambient temperature 6: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 7: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 8: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 9: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 10: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 11: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 12: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 13: NaIO4 / methanol; H2O / 22 h 14: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 15: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 16: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 17: dimethylformamide / 16 h / 40 °C 18: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 19: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 20: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 21 steps 1: pyridine / Ambient temperature 2: 75 percent AcOH / 1 h / 30 °C 3: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 4: NaOAc, Ac2O / 0.67 h / 130 °C 5: 1 percent NaOMe / methanol / 1 h / Ambient temperature 6: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 7: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 8: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 9: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 10: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 11: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 12: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 13: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 14: NaIO4 / methanol; H2O / 22 h 15: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 16: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 17: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 18: dimethylformamide / 16 h / 40 °C 19: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 20: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 21: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(3R,6RS)-6-(2-methoxyethoxymethoxy)-3-(1-methylethyl)-9-decenal dimethylacetal (113589-93-8) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 22 steps 1: OsO4, NaIO4 / diethyl ether; H2O / 7 h 2: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 3: pyridine / Ambient temperature 4: 75 percent AcOH / 1 h / 30 °C 5: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 6: NaOAc / 0.67 h / 130 °C 7: 1 percent NaOMe / methanol / 1 h / Ambient temperature 8: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 9: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 10: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 11: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 12: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 13: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 14: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 15: NaIO4 / methanol; H2O / 22 h 16: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 17: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 18: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 19: dimethylformamide / 16 h / 40 °C 20: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 21: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 22: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 23 steps 1: OsO4, NaIO4 / diethyl ether; H2O / 7 h 2: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 3: pyridine / Ambient temperature 4: 75 percent AcOH / 1 h / 30 °C 5: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 6: NaOAc / 0.67 h / 130 °C 7: 1 percent NaOMe / methanol / 1 h / Ambient temperature 8: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 9: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 10: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 11: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 12: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 13: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 14: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 15: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 16: NaIO4 / methanol; H2O / 22 h 17: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 18: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 19: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 20: dimethylformamide / 16 h / 40 °C 21: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 22: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 23: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 22 steps 1: OsO4, NaIO4 / diethyl ether; H2O / 7 h 2: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 3: pyridine / Ambient temperature 4: 75 percent AcOH / 1 h / 30 °C 5: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 6: NaOAc, Ac2O / 0.67 h / 130 °C 7: 1 percent NaOMe / methanol / 1 h / Ambient temperature 8: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 9: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 10: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 11: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 12: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 13: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 14: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 15: NaIO4 / methanol; H2O / 22 h 16: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 17: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 18: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 19: dimethylformamide / 16 h / 40 °C 20: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 21: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 22: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 23 steps 1: OsO4, NaIO4 / diethyl ether; H2O / 7 h 2: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 3: pyridine / Ambient temperature 4: 75 percent AcOH / 1 h / 30 °C 5: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 6: NaOAc, Ac2O / 0.67 h / 130 °C 7: 1 percent NaOMe / methanol / 1 h / Ambient temperature 8: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 9: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 10: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 11: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 12: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 13: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 14: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 15: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 16: NaIO4 / methanol; H2O / 22 h 17: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 18: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 19: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 20: dimethylformamide / 16 h / 40 °C 21: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 22: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 23: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(R)-2-Allyl-6-(2,2-dimethoxy-ethyl)-7-methyl-3-oxo-octanoic acid methyl ester (112193-61-0, 115042-30-3, 115042-31-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 25 steps 1: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 2: LiAlH4 / diethyl ether / 1 h / below 10 deg C 3: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 4: OsO4, NaIO4 / diethyl ether; H2O / 7 h 5: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 6: pyridine / Ambient temperature 7: 75 percent AcOH / 1 h / 30 °C 8: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 9: NaOAc / 0.67 h / 130 °C 10: 1 percent NaOMe / methanol / 1 h / Ambient temperature 11: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 12: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 13: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 14: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 15: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 16: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 17: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 18: NaIO4 / methanol; H2O / 22 h 19: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 20: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 21: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 22: dimethylformamide / 16 h / 40 °C 23: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 24: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 25: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 26 steps 1: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 2: LiAlH4 / diethyl ether / 1 h / below 10 deg C 3: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 4: OsO4, NaIO4 / diethyl ether; H2O / 7 h 5: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 6: pyridine / Ambient temperature 7: 75 percent AcOH / 1 h / 30 °C 8: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 9: NaOAc / 0.67 h / 130 °C 10: 1 percent NaOMe / methanol / 1 h / Ambient temperature 11: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 12: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 13: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 14: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 15: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 16: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 17: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 18: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 19: NaIO4 / methanol; H2O / 22 h 20: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 21: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 22: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 23: dimethylformamide / 16 h / 40 °C 24: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 25: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 26: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 25 steps 1: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 2: LiAlH4 / diethyl ether / 1 h / below 10 deg C 3: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 4: OsO4, NaIO4 / diethyl ether; H2O / 7 h 5: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 6: pyridine / Ambient temperature 7: 75 percent AcOH / 1 h / 30 °C 8: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 9: NaOAc, Ac2O / 0.67 h / 130 °C 10: 1 percent NaOMe / methanol / 1 h / Ambient temperature 11: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 12: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 13: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 14: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 15: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 16: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 17: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 18: NaIO4 / methanol; H2O / 22 h 19: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 20: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 21: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 22: dimethylformamide / 16 h / 40 °C 23: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 24: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 25: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 26 steps 1: 62 percent / 1.) KOH / methanol; H2O / 2 h / Heating 2: LiAlH4 / diethyl ether / 1 h / below 10 deg C 3: EtN(i-Pr)2 / CH2Cl2 / 24 h / Heating 4: OsO4, NaIO4 / diethyl ether; H2O / 7 h 5: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 6: pyridine / Ambient temperature 7: 75 percent AcOH / 1 h / 30 °C 8: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 9: NaOAc, Ac2O / 0.67 h / 130 °C 10: 1 percent NaOMe / methanol / 1 h / Ambient temperature 11: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 12: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 13: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 14: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 15: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 16: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 17: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 18: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 19: NaIO4 / methanol; H2O / 22 h 20: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 21: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 22: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 23: dimethylformamide / 16 h / 40 °C 24: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 25: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 26: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(R)-7-(2,2-Dimethoxy-ethyl)-4-(2-methoxy-ethoxymethoxy)-8-methyl-nonanal (113590-02-6) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 21 steps 1: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 2: pyridine / Ambient temperature 3: 75 percent AcOH / 1 h / 30 °C 4: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 5: NaOAc / 0.67 h / 130 °C 6: 1 percent NaOMe / methanol / 1 h / Ambient temperature 7: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 8: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 9: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 10: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 11: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 12: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 13: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 14: NaIO4 / methanol; H2O / 22 h 15: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 16: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 17: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 18: dimethylformamide / 16 h / 40 °C 19: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 20: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 21: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 22 steps 1: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 2: pyridine / Ambient temperature 3: 75 percent AcOH / 1 h / 30 °C 4: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 5: NaOAc / 0.67 h / 130 °C 6: 1 percent NaOMe / methanol / 1 h / Ambient temperature 7: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 8: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 9: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 10: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 11: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 12: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 13: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 14: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 15: NaIO4 / methanol; H2O / 22 h 16: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 17: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 18: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 19: dimethylformamide / 16 h / 40 °C 20: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 21: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 22: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 21 steps 1: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 2: pyridine / Ambient temperature 3: 75 percent AcOH / 1 h / 30 °C 4: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 5: NaOAc, Ac2O / 0.67 h / 130 °C 6: 1 percent NaOMe / methanol / 1 h / Ambient temperature 7: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 8: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 9: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 10: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 11: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 12: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 13: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 14: NaIO4 / methanol; H2O / 22 h 15: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 16: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 17: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 18: dimethylformamide / 16 h / 40 °C 19: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 20: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 21: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 22 steps 1: LiAlH4 / diethyl ether / 0.5 h / below 10 deg C 2: pyridine / Ambient temperature 3: 75 percent AcOH / 1 h / 30 °C 4: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 5: NaOAc, Ac2O / 0.67 h / 130 °C 6: 1 percent NaOMe / methanol / 1 h / Ambient temperature 7: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 8: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 9: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 10: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 11: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 12: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 13: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 14: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 15: NaIO4 / methanol; H2O / 22 h 16: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 17: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 18: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 19: dimethylformamide / 16 h / 40 °C 20: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 21: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 22: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(4S,5E)-4-isopropyl-7-methylene-10-phenylthio-5-cyclodecen-1-one (90460-45-0, 105371-09-3, 113666-99-2) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 8 steps 1: NaIO4 / methanol; H2O / 22 h 2: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 3: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 4: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 5: dimethylformamide / 16 h / 40 °C 6: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 7: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 8: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

Acetic acid (R)-4-(2-methoxy-ethoxymethoxy)-8-methyl-7-(2-oxo-ethyl)-nonyl ester (113589-94-9) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 18 steps 1: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 2: NaOAc / 0.67 h / 130 °C 3: 1 percent NaOMe / methanol / 1 h / Ambient temperature 4: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 5: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 6: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 7: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 8: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 9: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 10: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 11: NaIO4 / methanol; H2O / 22 h 12: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 13: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 14: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 15: dimethylformamide / 16 h / 40 °C 16: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 17: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 18: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 19 steps 1: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 2: NaOAc / 0.67 h / 130 °C 3: 1 percent NaOMe / methanol / 1 h / Ambient temperature 4: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 5: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 6: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 7: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 8: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 9: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 10: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 11: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 12: NaIO4 / methanol; H2O / 22 h 13: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 14: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 15: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 16: dimethylformamide / 16 h / 40 °C 17: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 18: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 19: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 18 steps 1: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 2: NaOAc, Ac2O / 0.67 h / 130 °C 3: 1 percent NaOMe / methanol / 1 h / Ambient temperature 4: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 5: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 6: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 7: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 8: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 9: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 10: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 11: NaIO4 / methanol; H2O / 22 h 12: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 13: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 14: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 15: dimethylformamide / 16 h / 40 °C 16: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 17: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 18: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 19 steps 1: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 2: NaOAc, Ac2O / 0.67 h / 130 °C 3: 1 percent NaOMe / methanol / 1 h / Ambient temperature 4: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 5: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 6: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 7: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 8: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 9: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 10: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 11: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 12: NaIO4 / methanol; H2O / 22 h 13: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 14: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 15: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 16: dimethylformamide / 16 h / 40 °C 17: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 18: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 19: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(3R,6RS)-9-acetoxy-6-(2-methoxyethoxymethoxy)-3-(1-methylethyl)-nonanal dimethylacetal (113603-27-3) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 19 steps 1: 75 percent AcOH / 1 h / 30 °C 2: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 3: NaOAc / 0.67 h / 130 °C 4: 1 percent NaOMe / methanol / 1 h / Ambient temperature 5: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 6: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 7: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 8: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 9: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 10: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 11: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 12: NaIO4 / methanol; H2O / 22 h 13: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 14: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 15: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 16: dimethylformamide / 16 h / 40 °C 17: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 18: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 19: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 20 steps 1: 75 percent AcOH / 1 h / 30 °C 2: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 3: NaOAc / 0.67 h / 130 °C 4: 1 percent NaOMe / methanol / 1 h / Ambient temperature 5: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 6: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 7: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 8: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 9: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 10: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 11: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 12: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 13: NaIO4 / methanol; H2O / 22 h 14: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 15: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 16: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 17: dimethylformamide / 16 h / 40 °C 18: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 19: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 20: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 19 steps 1: 75 percent AcOH / 1 h / 30 °C 2: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 3: NaOAc, Ac2O / 0.67 h / 130 °C 4: 1 percent NaOMe / methanol / 1 h / Ambient temperature 5: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 6: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 7: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 8: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 9: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 10: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 11: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 12: NaIO4 / methanol; H2O / 22 h 13: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 14: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 15: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 16: dimethylformamide / 16 h / 40 °C 17: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 18: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 19: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 20 steps 1: 75 percent AcOH / 1 h / 30 °C 2: 1.) LDA / 1.) THF, below -60 deg C, 20 min; 2.) THF, below -60 deg C, 30 min 3: NaOAc, Ac2O / 0.67 h / 130 °C 4: 1 percent NaOMe / methanol / 1 h / Ambient temperature 5: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 6: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 7: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 8: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 9: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 10: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 11: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 12: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 13: NaIO4 / methanol; H2O / 22 h 14: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 15: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 16: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 17: dimethylformamide / 16 h / 40 °C 18: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 19: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 20: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(4S,5E)-7-methylene-4-(1-methylethyl)-10-phenylsulfinyl-5-cyclodecene-1-one (105329-29-1, 105371-14-0, 113666-32-3) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 2: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 3: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 4: dimethylformamide / 16 h / 40 °C 5: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 6: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 7: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

(1RS,2E,4S,7RS)-7-(2-methoxyethoxymethoxy)-4-(1-methylethyl)-1-phenylthio-2-cyclodecene-1-methanol (113603-28-4) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions

Yield

Multi-step reaction with 13 steps 1: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 2: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 3: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 4: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 5: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 6: NaIO4 / methanol; H2O / 22 h 7: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 8: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 9: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 10: dimethylformamide / 16 h / 40 °C 11: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 12: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 13: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

methyl (2EZ,5R,8RS)-11-hydroxy-8-(2-methoxyethoxymethoxy)-5-(1-methylethyl)-2-phenylthio-2-undeceonate (113589-96-1) → (3S,8R,9R,10S)-(-)-periplanone-B (61228-92-0)

Conditions	Yield
Multi-step reaction with 15 steps 1: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 2: 1.) NaN(TMS)2; 2.) LiAlH4 / 1.) DME, 50 min, reflux; 2.) Et2O, 0 deg C, 1 h 3: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 4: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 5: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 6: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 7: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 8: NaIO4 / methanol; H2O / 22 h 9: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 10: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 11: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 12: dimethylformamide / 16 h / 40 °C 13: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 14: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 15: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme
Multi-step reaction with 16 steps 1: 97 percent / Et3N, DMAP / CH2Cl2 / 7 h / below 0 deg C 2: NaN(TMS)2 / 1,2-dimethoxy-ethane / 0.83 h / Heating 3: 99 percent / LiAlH4 / diethyl ether / 1 h / 0 °C 4: DMAP, pyridine / tetrahydrofuran / 24 h / Ambient temperature 5: 84 percent / TMSCl, NaI / acetonitrile / -10 °C 6: 86 percent / sodium naphtalenide / 0.08 h / -70 °C 7: 69 percent / PCC, molecular sieves 3A / CH2Cl2 / 0.5 h / Ambient temperature 8: 1.) hexamethyldisilazane, n-BuLi / 1.) THF, n-hexane, -10 deg C, 10 min; 2.) THF, -70 deg C, 1 h; 3.) THF, -5 to 20 deg C, 5 min 9: NaIO4 / methanol; H2O / 22 h 10: 2,6-di-t-butyl-p-cresol (BHT), CaCO3 / toluene / 6 h / Heating 11: 1.) KH, t-BuOOH / 1.) THF, toluene, below -5 deg C, 5 min; 2.) THF, 0 deg C, 1 h 12: 1.) LiN(TMS)2; 2.) MoO5*HMPA*C5H5N / 1.) THF, -70 deg C, 1 h; 2.) -22 deg C, 15 min 13: dimethylformamide / 16 h / 40 °C 14: 1.) n-BuLi / 1. THF, n-hexane, RT, 10 min; 2.) THF, -5 deg C, 10 min 15: n-Bu4NF / tetrahydrofuran / 0.17 h / Ambient temperature 16: 88 percent / PCC, molecular sieves 3A / CH2Cl2 / 1 h / Ambient temperature View Scheme

Upstream product

• 70800-65-6 Periplanol B 
• 70800-65-6 (1S,3S,4E,8R,9R,10S)-8,9-epoxy-10,10-epoxymethano-3-isopropyl-6-methylene-4-cyclodecen-1-ol 
• 105930-39-0 (4S,5E,9R,10R)-9,10-epoxy-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one 
• 113666-35-6 (2S,4S,5E,9R,10R)-2-t-butyldimethylsilyloxy-9,10-epoxy-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one 
• 70552-76-0 (1S,3S,4E,8R,9R,10R)-1-t-butyldimethylsilyloxy-8,9-epoxy-6-methylene-10,10-methylenoxy-3-(1-methylethyl)-4-cyclodecene 
• 105930-38-9 (4S,5E)-7-methylene-4-(1-methylethyl)-5-cyclodecene-1-one 
• 590-86-3 isovaleraldehyde 
• 103002-89-7 (E)-(1R,5S,10R)-3-Hydroxy-5-isopropyl-8-methylene-11-oxa-bicyclo[8.1.0]undec-6-en-2-one 
• 6814-64-8 methylenedimethyl sulfurane 
• 105930-41-4 (E)-(1R,5S,10R)-5-Isopropyl-8-methylene-11-oxa-bicyclo[8.1.0]undec-6-ene-2,3-dione 
• 105897-83-4 (1S,5S,6R)-6-((E)-3-Methyl-but-1-enyl)-5-(tetrahydro-pyran-2-yloxymethyl)-1-vinyl-cyclohex-2-enol 
• 105897-82-3 (5S,6R)-6-((E)-3-Methyl-but-1-enyl)-5-(tetrahydro-pyran-2-yloxymethyl)-cyclohex-2-enone 
• 103002-80-8 Toluene-4-sulfonic acid (4E,8Z)-(3R,6R)-6-(tert-butyl-diphenyl-silanyloxymethyl)-10-cyano-10-(1-ethoxy-ethoxy)-3-isopropyl-deca-4,8-dienyl ester 
• 112538-42-8 Toluene-4-sulfonic acid (E)-(3R,6R)-6-(tert-butyl-diphenyl-silanyloxymethyl)-10-hydroxy-3-isopropyl-dec-4-en-8-ynyl ester 

Relevant articles and documents

Synthesis of (-)-periplanone-B, a sex pheromone component of the American cockroach (Periplaneta americana)

The naturally occurring (-)-enantiomer of periplanone-B was synthesized stereoselectively starting from (S)-3-cyclohexene-1-carboxylic acid. The crystalline pheromone was obtained in 12% overall yield through 18 steps.

TOTAL SYNTHESIS OF (-)-PERIPLANONE-B, NATURAL MAJOR SEX-EXCITANT PHEROMONE OF THE AMERICAN COCKROACH, PERIPLANETA AMERICANA

The total synthesis of (-)-periplanone-B 1, the major sex excitant and attractant pheromone of the American cockroach was accomplished starting from (+)-dihydrolimonene 2.Intramolecular alkylation of the substituted α-phenylthioacrylate 10 gave rise to the (E)-cyclodecene 11.Second key reaction was the reductive elimination of vicinal phenylthiobenzoate 14 to provide the cojugated diene 15.Overall yield of 1 through 28 steps was 0.5 percent.

TOTAL SYNTHESIS OF (-)-PERIPLANONE-B, THE SEX PHEROMONE OF THE AMERICAN COCKROACH

The total synthesis of (-)-periplanone-B, the sex excitant pheromone of the American cockroach, Periplaneta americana is accomplished starting from (+)-limonene.