489-39-4

Basic information

• Product Name: (+)-AROMADENDRENE
• Synonyms: 1H-Cycloprop[e]azulene, decahydro-1,1,7-trimethyl-4-methylene-, (1aR,4aR,7R,7aR,7bS)-(+)-;aromandendrene;(+)-AROMADENDRENE;AROMADENDRENE, (+);(1R,2S,8R,11R)-7-METHYLENE-3,3,11-TRIMETHYL-TRICYCLO[6.3.0.0(2.4)]UNDECANE;[1aR-(1aalpha,4aalpha,7alpha,7abeta,7balpha)]-decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop[e]azulene;aromadendrene,aromadendrene,[1ar-(1aalpha,4aalpha,7alpha,7abeta,7balpha)]-decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop[e]azulene;AROMADENDRENE, (+)-(SG)
• CAS NO: 489-39-4
• Molecular Formula: C₁₅H₂₄
• Molecular Weight: 204.35
• EINECS: 207-694-6
• Mol File: 489-39-4.mol
• Article Data: 4

Chemical Properties

• Melting Point: 262°C
• Boiling Point: 261-263 °C(lit.)
• Flash Point: 90℃
• Appearance: /
• Density: 0.912 g/mL at 20 °C(lit.)
• Refractive Index: n20/D 1.497
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Soluble), Ethyl Acetate (Slightly), Methanol (Slightly)
• BRN: 2554306
• CAS DataBase Reference: (+)-AROMADENDRENE(CAS DataBase Reference)
• NIST Chemistry Reference: (+)-AROMADENDRENE(489-39-4)
• EPA Substance Registry System: (+)-AROMADENDRENE(489-39-4)

Safety Data

• WGK Germany: 3
• F: 10-23
• Hazardous Substances Data: 489-39-4(Hazardous Substances Data)

Usage

Uses

(+)-Aromadendrene may be used as a chiral starting material to synthesize other sesquiterenes such as (-)-apoaromadendrone, (-)-kessane, (+)-spathulenol, (+)-ledene and (-)-isoledene.

General Description

(+)-Aromadendrene, a sesquiterpenoid, is the major constituent of the essential oil of Eucalypfus globulus.

Synthetic route

Methanesulfonic acid (1aR,4S,4aR,7R,7aR,7bS)-1,1,7-trimethyl-decahydro-cyclopropa[e]azulen-4-ylmethyl ester (175985-51-0) → (+)-aromadendrene (489-39-4)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 100℃; for 18h;	89%

(1aR,4aR,7R,7aS,7bS)-1,1,7-Trimethyldecahydro-4H-cyclopropa[e]azulen-4-one (99147-41-8) + Methyltriphenylphosphonium bromide (1779-49-3) → (+)-aromadendrene (489-39-4)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 0.166667h; Inert atmosphere; Stage #2: (1aR,4aR,7R,7aS,7bS)-1,1,7-Trimethyldecahydro-4H-cyclopropa[e]azulen-4-one In tetrahydrofuran at -78 - 20℃; for 24h; Inert atmosphere;	60%

(-)-globulol (489-41-8) → (+)-aromadendrene (489-39-4)

Conditions	Yield
With pyridine; trichlorophosphate

(-)-O-<3,5-dinitro-benzoyl>-globulol → (+)-aromadendrene (489-39-4)

Conditions	Yield
at 140℃; unter vermindertem Druck;

methyl (+)-(1S,7R)-8,8-dimethyl-3-oxobicyclo<5.1.0>octane-4-carboxylate (176199-11-4) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 15 steps 1: 100 percent / LiAlH4 / diethyl ether / 1 h / Ambient temperature 2: imidazole / dimethylformamide / 12 h / Ambient temperature 3: 90 percent / Ley's tetrapropylammonium perruthenate, 4-methylmorpholine N-oxide, molecular sieves / CH2Cl2 / 0.25 h / Ambient temperature 4: 1.) LDA, HMPA / 1.) THF, -78 deg C, 30 min, 2.) THF, from -78 deg C to RT, 4 h 5: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 6: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 7: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 8: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 9: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 10: NaBH4 / methanol / 2 h / Ambient temperature 11: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 12: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 13: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 14: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 15: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1S,7R)-4-Hydroxymethyl-8,8-dimethyl-bicyclo[5.1.0]octan-3-ol → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 14 steps 1: imidazole / dimethylformamide / 12 h / Ambient temperature 2: 90 percent / Ley's tetrapropylammonium perruthenate, 4-methylmorpholine N-oxide, molecular sieves / CH2Cl2 / 0.25 h / Ambient temperature 3: 1.) LDA, HMPA / 1.) THF, -78 deg C, 30 min, 2.) THF, from -78 deg C to RT, 4 h 4: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 5: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 6: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 7: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 8: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 9: NaBH4 / methanol / 2 h / Ambient temperature 10: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 11: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 12: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 13: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 14: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1aR,4S,4aR,7S,7aR,7bS)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-1,1,7-trimethyl-decahydro-cyclopropa[e]azulen-6-ol → (+)-aromadendrene (489-39-4)

Conditions	Yield
Multi-step reaction with 5 steps 1: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 2: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 3: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 4: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 5: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(+)-(1S,2S,4R,7R)-4-tert-butyldimethylsiloxymethyl-8,8-dimethyl-2-(2-propenyl)bicyclo<5.1.0>octan-3-one (175985-40-7) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 11 steps 1: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 2: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 3: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 4: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 5: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 6: NaBH4 / methanol / 2 h / Ambient temperature 7: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 8: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 9: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 10: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 11: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(+)-(1R,2S,4R,7S,8R,11S)-7-tert-butyldimethylsiloxymethyl-3,3,11-trimethyltricyclo<6.3.0.02,4>undecan-10-one (175985-45-2) → (+)-aromadendrene (489-39-4)

Conditions	Yield
Multi-step reaction with 6 steps 1: NaBH4 / methanol / 2 h / Ambient temperature 2: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 3: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 4: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 5: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 6: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(+)-(1R,2R,4R,7S)-7-tert-butyldimethylsiloxymethyl-3,3-dimethyltricyclo<6.3.0.02,4>undec-8-en-10-one (175985-44-1) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 9 steps 1: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 2: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 3: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 4: NaBH4 / methanol / 2 h / Ambient temperature 5: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 6: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 7: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 8: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 9: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(+)-(1S,2S,4R,7R)-4-tert-butyldimethylsiloxymethyl-8,8-dimethyl-2-(2-oxopropyl)bicyclo<5.1.0>octan-3-one (175985-43-0) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 10 steps 1: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 2: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 3: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 4: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 5: NaBH4 / methanol / 2 h / Ambient temperature 6: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 7: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 8: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 9: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 10: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1R,2S,4R,7S,8R,11S)-7-tert-butyldimethylsiloxymethyl-3,3,11-trimethyltricyclo<6.3.0.02,4>undec-10-yl phenyl thionocarbonate → (+)-aromadendrene (489-39-4)

Conditions	Yield
Multi-step reaction with 4 steps 1: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 2: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 3: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 4: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

((1aR,4S,4aR,7R,7aR,7bS)-1,1,7-trimethyldecahydro-1H-cyclopropa[e]azulen-4-yl)methanol (175985-50-9) → (+)-aromadendrene (489-39-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 2: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(+)-(1S,4RS,7R)-8,8-dimethyl-4-hydroxymethylbicyclo[5.1.0]octan-3-one → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 15 steps 1: LiAlH4 / diethyl ether / 0.25 h / 0 °C 2: imidazole / dimethylformamide / 12 h / Ambient temperature 3: 90 percent / Ley's tetrapropylammonium perruthenate, 4-methylmorpholine N-oxide, molecular sieves / CH2Cl2 / 0.25 h / Ambient temperature 4: 1.) LDA, HMPA / 1.) THF, -78 deg C, 30 min, 2.) THF, from -78 deg C to RT, 4 h 5: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 6: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 7: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 8: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 9: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 10: NaBH4 / methanol / 2 h / Ambient temperature 11: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 12: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 13: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 14: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 15: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1S,4R,7R)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-8,8-dimethyl-bicyclo[5.1.0]octan-3-ol → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 13 steps 1: 90 percent / Ley's tetrapropylammonium perruthenate, 4-methylmorpholine N-oxide, molecular sieves / CH2Cl2 / 0.25 h / Ambient temperature 2: 1.) LDA, HMPA / 1.) THF, -78 deg C, 30 min, 2.) THF, from -78 deg C to RT, 4 h 3: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 4: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 5: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 6: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 7: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 8: NaBH4 / methanol / 2 h / Ambient temperature 9: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 10: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 11: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 12: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 13: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

tert-Butyl-dimethyl-((1aR,4S,4aR,7R,7aR,7bS)-1,1,7-trimethyl-decahydro-cyclopropa[e]azulen-4-ylmethoxy)-silane (175985-49-6) → (+)-aromadendrene (489-39-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 2: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 3: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1S,4R,7R)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-8,8-dimethyl-bicyclo[5.1.0]octan-3-one (175985-39-4) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 12 steps 1: 1.) LDA, HMPA / 1.) THF, -78 deg C, 30 min, 2.) THF, from -78 deg C to RT, 4 h 2: 96 percent / PdCl2, CuCl, air / dimethylformamide; H2O / 4.5 h / Ambient temperature 3: 84 percent / NaHMDS, HMPA / tetrahydrofuran / 0.67 h / -78 - -50 °C / a) -78 deg C. 15 min, b) 0 deg C, 15 min, c) 50 deg C, 10 min 4: 1.) lithium hexamethyldisilazane, HMPA / 1.) THF, -78 deg C, 1 h, 2.) THF, from -78 deg C to RT, 2 h 5: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 6: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 7: NaBH4 / methanol / 2 h / Ambient temperature 8: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 9: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 10: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 11: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 12: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1aR,4S,7S,7aR,7bR)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-1,1,7-trimethyl-1a,3,4,7,7a,7b-hexahydro-1H,2H-cyclopropa[e]azulen-6-one (176199-13-6) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 7 steps 1: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 2: NaBH4 / methanol / 2 h / Ambient temperature 3: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 4: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 5: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 6: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 7: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

(1aR,4S,7R,7aR,7bR)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-1,1,7-trimethyl-1a,3,4,7,7a,7b-hexahydro-1H,2H-cyclopropa[e]azulen-6-one (175985-37-2) → (+)-aromadendrene (489-39-4)

Conditions

Yield

Multi-step reaction with 8 steps 1: 86 percent / lithium tetramethyldisilazane, HMPA / tetrahydrofuran / 2 h / -78 - 20 °C 2: 93 percent / H2 / 5percent Pd/C / methanol / 2 h / 760 Torr / Ambient temperature 3: NaBH4 / methanol / 2 h / Ambient temperature 4: pyridine, DMAP / CH2Cl2 / 6 h / Ambient temperature 5: 68 percent / n-Bu3SnH, AIBN / toluene / 3 h / Heating 6: 100 percent / tetra-n-butylammonium fluoride / tetrahydrofuran / 6 h / Ambient temperature 7: 100 percent / Et3N, DMAP / CH2Cl2 / 2 h / 0 °C 8: 89 percent / DBU / toluene / 18 h / 100 °C View Scheme

thiocyanic acid (463-56-9) + (+)-aromadendrene (489-39-4) → (-)-10(R)-Isothiocyanoaromadendrane (56012-90-9)

Conditions	Yield
In chloroform for 48h; Ambient temperature;	97%
for 48h; Ambient temperature;	96.6%
In chloroform at 20℃; for 48h;	74%

(+)-aromadendrene (489-39-4) → (1aR,4R,7R,7bS)-1,1,4,7-tetramethyl-1a,2,3,4,5,6,7,7b-octahydro-1H-cyclopropa[e]azulene (29484-27-3, 95910-36-4, 110769-61-4)

Conditions	Yield
With aluminum oxide at 100℃;	96%
With aluminum oxide; potassium In hexane at 0 - 20℃; for 12h;	71%

(+)-aromadendrene (489-39-4) → [1aR-(1aα,7α,7aβ,7bα)]-1a,2,3,5,6,7,7a,7b-octahydro-1,1,4,7-tetramethyl-1H-cycloprop[e]azulene (74409-93-1, 77171-52-9, 128779-67-9, 21747-46-6)

Conditions	Yield
With potassium tert-butylate In dimethyl sulfoxide at 100℃;	80%

(+)-aromadendrene (489-39-4) → (1aR)-4ξ-hydroxymethyl-1,1,7c-trimethyl-(1ar,4ac,7at,7bc)-decahydro-cycloprop[e]azulen-4ξ-ol (95924-99-5, 97950-11-3, 145988-09-6)

Conditions	Yield
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In water; tert-butyl alcohol at 20℃; for 64h;	79%
With potassium permanganate In acetone
(i) OsO4, Et2O, (ii) aq. KOH, benzene, EtOH, mannitol; Multistep reaction;

(+)-aromadendrene (489-39-4) + phenylselenyl triflate (112238-64-9) → C21H30OSe (1114568-42-1) + C21H30OSe (1114568-41-0)

Conditions	Yield
With water In acetonitrile at 0 - 20℃; for 40h; optical yield given as %de;	A 56% B 40%

(+)-aromadendrene (489-39-4) + phenylselenyl triflate (112238-64-9) → (((1aR,4R,4aR,7R,7aS,7bS)-4-azido-1,1,7-trimethyldecahydro-1H-cyclopropa[e]azulen-4-yl)methyl)(phenyl)selane + (((1aR,4S,4aR,7R,7aS,7bS)-4-azido-1,1,7-trimethyldecahydro-1H-cyclopropa[e]azulen-4-yl)methyl)(phenyl)selane

Conditions	Yield
Stage #1: phenylselenyl triflate With sodium azide In chloroform at 0℃; for 0.5h; Stage #2: (+)-aromadendrene In acetonitrile at 20℃; for 30h; Further stages.;	A 54% B 16%

(+)-aromadendrene (489-39-4) → C15H24O3 + C15H24O3

Conditions	Yield
Stage #1: (+)-aromadendrene With ferrous(II) sulfate heptahydrate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ozone In methanol; water at -78 - 20℃; for 0.0833333h; Stage #2: With magnesium bis(monoperoxyphthalate)hexahydrate In methanol; water at 0℃; for 2h;	A 54% B 37%

(+)-aromadendrene (489-39-4) → (1aR,4aR,7R,7aS,7bS)-1,1,7-Trimethyldecahydro-4H-cyclopropa[e]azulen-4-one (99147-41-8)

Conditions	Yield
Stage #1: (+)-aromadendrene With sodium hydrogencarbonate; ozone In methanol; dichloromethane at -78℃; for 0.5h; Stage #2: With triphenylphosphine In methanol; dichloromethane at 20℃; Inert atmosphere;	43%
With ozone
Multi-step reaction with 2 steps 1: O3 / pentane / -45 °C 2: 95 percent / Ph3P / CDCl3 View Scheme
Multi-step reaction with 2 steps 1: aq. KMnO4 / acetone 2: aq. NaIO4 / methanol View Scheme
Multi-step reaction with 2 steps 1: 4-methylmorpholine N-oxide; osmium(VIII) oxide / tert-butyl alcohol; water / 64 h / 20 °C 2: sodium periodate / water; methanol / 2 h / 20 °C / Inert atmosphere View Scheme

(+)-aromadendrene (489-39-4) → (1R,2S,6S,7S,10R)-3-Isopropyl-6,10-dimethyltricyclo[5.3.0.02,7]dec-3-ene

Conditions	Yield
With hexane; fluorosulfonylchloride; silver nitrate at -115 - -110℃;	26%

isocyanate de chlorosulfonyle (1189-71-5) + (+)-aromadendrene (489-39-4) → C16H25NO

Conditions	Yield
Stage #1: isocyanate de chlorosulfonyle; (+)-aromadendrene In dichloromethane at 23℃; for 2h; Stage #2: With triethylamine In dichloromethane at 23℃; for 3h; Stage #3: With water In dichloromethane at 23℃; for 24h; diastereoselective reaction;	25%

(+)-aromadendrene (489-39-4) → (1S,2S,4R,7R,8R,11R)-3,3,11-trimethyl-7-hydroxymethyl-tricyclo<6.3.0.02,4>undecan-7-ol (145988-09-6) + (1S,2S,3S,4R,7R,8R,11R)-3,7-bis(hydroxymethyl)-3,11-dimethyltricyclo<6.3.0.02,4>undecan-7-ol (145988-10-9)

Conditions	Yield
In N,N-dimethyl-formamide for 168h; Bacillus megaterium DSM 32;	A 4 mg B 7 mg

(+)-aromadendrene (489-39-4) → Nitrosochlorid von Aromadendren

Conditions	Yield
With nitrosylchloride

methanol (67-56-1) + (+)-aromadendrene (489-39-4) → (1R,2S,6S,7S,10R)-3-Isopropyl-3-methoxy-6,10-dimethyltricyclo[5.3.0.02,7]decane + (1R,2S,6S,7S,10R)-3-Isopropyl-6,10-dimethyltricyclo[5.3.0.02,7]dec-3-ene

Conditions	Yield
With fluorosulfonylchloride at -115 - -110℃;	A 65 % Chromat. B 18 % Chromat.
With fluorosulfonylchloride; fluorosulphonic acid 2.) (C2H5)2O; Yield given. Multistep reaction. Yields of byproduct given;

(+)-aromadendrene (489-39-4) → (1R,3S,7S,8S)-2,2,4,8-tetramethyltricyclo<5.3.1.03.7>undec-4-ene

Conditions	Yield
With formic acid Heating; Yield given;

(+)-aromadendrene (489-39-4) → (1R,2S,6S,7S,10R)-3-Isopropyl-3-methoxy-6,10-dimethyltricyclo[5.3.0.02,7]decane + (1R,2S,6S,7S,10R)-3-Isopropyl-6,10-dimethyltricyclo[5.3.0.02,7]dec-3-ene

Conditions	Yield
With methanol; fluorosulfonylchloride; fluorosulphonic acid 2.) (C2H5)2O; Yield given. Multistep reaction. Yields of byproduct given;

(+)-aromadendrene (489-39-4) → (1R,3S,7S,8S)-2,2,4,8-tetramethyltricyclo[5.3.1.03,7]undec-4-ene

Conditions	Yield
With formic acid Heating; Yield given;

(+)-aromadendrene (489-39-4) → (+)-aromadendrene ozonide

Conditions	Yield
With ozone In pentane at -45℃;

(+)-aromadendrene (489-39-4) → (1S,2S,4R,7R,8R,11R)-3,3,11-trimethyl-7-hydroxymethyl-tricyclo<6.3.0.02,4>undecan-7-ol (145988-09-6)

Conditions	Yield
With osmium(VIII) oxide; potassium carbonate; potassium hexacyanoferrate(III) In water; tert-butyl alcohol for 24h; Ambient temperature;	900 mg

(+)-aromadendrene (489-39-4) → 7-isopropyl-1,4-dimethyl-azulene (489-84-9)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 96 percent / K/Al2O3 / 100 °C 2.1: BF3*Et2O / CH2Cl2 / 3 h / 20 °C 2.2: 42 mg / sulfur / 1,3,5-trimethyl-benzene / 160 °C View Scheme

(+)-aromadendrene (489-39-4) → (1aR,4S,7R,7aS,7bR)-1,1,4,7-tetramethyl-1a,2,3,4,6,7,7a,7b-octahydro-1H-cyclopropa[e]azulen-4-ol (63181-42-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 80 percent / KOtBu / dimethylsulfoxide / 100 °C 2: 96 percent / oxone; NaHCO3; 18-crown-6 / CH2Cl2; H2O; acetone / 2 h / 0 °C 3: 57 percent / diethylamine; n-butyllithium / diethyl ether; hexane / 0 - 20 °C View Scheme

(+)-aromadendrene (489-39-4) → (1aR,4S,4aR,7R,7aS,7bR)-1,1,4,7-tetramethyldecahydro-4aH-cyclopropa[e]azulene-4,4a-diol (6894-71-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / KOtBu / dimethylsulfoxide / 100 °C 2: 54 percent / KMnO4 / ethanol; H2O / 2 h / 0 °C View Scheme

(+)-aromadendrene (489-39-4) → (2aR,8R,8aR,8bR)-2,2,5,8-tetramethyl-2a,3,4,6,7,8,8a,8b-octahydro-2H-naphtho[1,8-bc]furan

Conditions	Yield
Multi-step reaction with 3 steps 1: 80 percent / KOtBu / dimethylsulfoxide / 100 °C 2: 54 percent / KMnO4 / ethanol; H2O / 2 h / 0 °C 3: acetic acid; iodine / tetrahydrofuran; H2O / 96 h / 20 °C View Scheme
Multi-step reaction with 3 steps 1: 80 percent / KOtBu / dimethylsulfoxide / 100 °C 2: 96 percent / oxone; NaHCO3; 18-crown-6 / CH2Cl2; H2O; acetone / 2 h / 0 °C 3: 45 percent / sulfuric acid / tetrahydrofuran; H2O / 2 h / 30 °C View Scheme

(+)-aromadendrene (489-39-4) → (1R,3aR,4aS,6aR,7aR,7bS)-1,4a,7,7-tetramethyldecahydrocyclopropa[7,8]azuleno[3a,4-b]oxirene (178602-94-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / KOtBu / dimethylsulfoxide / 100 °C 2: 96 percent / oxone; NaHCO3; 18-crown-6 / CH2Cl2; H2O; acetone / 2 h / 0 °C View Scheme

Upstream product

• 141564-33-2 Trimethyl-((1aR,7R,7aS,7bR)-1,1,7-trimethyl-1a,2,3,5,6,7,7a,7b-octahydro-1H-cyclopropa[e]azulen-4-yloxy)-silane 
• 6790-66-5 (-)-apoaromadendrone 
• 27200-84-6 methyl triphenylphosphonium bromide 
• 99147-41-8 (1aR,4aR,7R,7aS,7bS)-1,1,7-Trimethyldecahydro-4H-cyclopropa[e]azulen-4-one 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 175985-37-2 (1aR,4S,7R,7aR,7bR)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-1,1,7-trimethyl-1a,3,4,7,7a,7b-hexahydro-1H,2H-cyclopropa[e]azulen-6-one 
• 176199-13-6 (1aR,4S,7S,7aR,7bR)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-1,1,7-trimethyl-1a,3,4,7,7a,7b-hexahydro-1H,2H-cyclopropa[e]azulen-6-one 
• 175985-39-4 (1S,4R,7R)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-8,8-dimethyl-bicyclo[5.1.0]octan-3-one 
• 175985-49-6 tert-Butyl-dimethyl-((1aR,4S,4aR,7R,7aR,7bS)-1,1,7-trimethyl-decahydro-cyclopropa[e]azulen-4-ylmethoxy)-silane 
• 175985-50-9 ((1aR,4S,4aR,7R,7aR,7bS)-1,1,7-trimethyldecahydro-1H-cyclopropa[e]azulen-4-yl)methanol 
• 175985-43-0 (+)-(1S,2S,4R,7R)-4-tert-butyldimethylsiloxymethyl-8,8-dimethyl-2-(2-oxopropyl)bicyclo<5.1.0>octan-3-one 
• 175985-44-1 (+)-(1R,2R,4R,7S)-7-tert-butyldimethylsiloxymethyl-3,3-dimethyltricyclo<6.3.0.0^2,4>undec-8-en-10-one 
• 175985-45-2 (+)-(1R,2S,4R,7S,8R,11S)-7-tert-butyldimethylsiloxymethyl-3,3,11-trimethyltricyclo<6.3.0.0^2,4>undecan-10-one 
• 175985-40-7 (+)-(1S,2S,4R,7R)-4-tert-butyldimethylsiloxymethyl-8,8-dimethyl-2-(2-propenyl)bicyclo<5.1.0>octan-3-one 

Downstream Products

• 1114568-42-1 C₂₁H₃₀OSe 
• 1114568-41-0 C₂₁H₃₀OSe 
• 6750-60-3 spathulenol 
• 99147-42-9 (+)-11β-hydroxy-apoaromadendrone 
• 22567-17-5 [1R-(1α,3aβ,4α,7β)]-1,2,3,3a,4,5,6,7-octahydro-1,4-dimethyl-7-(1-methylethenyl)-azulene 
• 186318-55-8 Toluene-4-sulfonic acid (1aR,4R,4aR,7R,7aS,7bS)-4-hydroxy-1,1,7-trimethyl-decahydro-cyclopropa[e]azulen-4-ylmethyl ester 
• 489-84-9 7-isopropyl-1,4-dimethyl-azulene 
• 74409-93-1 [1aR-(1aα,7α,7aβ,7bα)]-1a,2,3,5,6,7,7a,7b-octahydro-1,1,4,7-tetramethyl-1H-cycloprop[e]azulene 
• 29484-27-3 (1aR,4R,7R,7bS)-1,1,4,7-tetramethyl-1a,2,3,4,5,6,7,7b-octahydro-1H-cyclopropa[e]azulene 
• 56012-90-9 (+)-axisothiocyanate 2 

Relevant articles and documents

Synthetic studies on aromadendrane-type compounds. III. Stereoselective total syntheses of (+)-aromadendrene and (-)-alloaromadendrene

The stereoselective total syntheses of (+)-aromadendrene (5) and (-)-alloaromadendrene (6) were achieved via (+)-(1S,2R,4R,7S,11R)-7-tert-butyldimethylsiloxymethyl-3,3,11-trimethy ltricyclo[6.3.0.02,4]undec-8-en-10-one (7) as a common intermediate.

The synthesis of mono- and dihydroxy aromadendrane sesquiterpenes, starting from natural (+)-aromadendrene-III

The monoalcohols (-)-globulol (2), (-)-epiglobulol (3), (-)-ledol (4), and (+)-viridiflorol (5) were synthesized from (+)-aromadendrene (1). The cis-fused alloaromandedrone (14), the key intermediate used in the synthesis of 4 and 5, was obtained from the trans-fused apoaromadendrone (13) via a selective protonation of the thermodynamic enol trimethylsilylether 15. After hydroxylation of the tertiary C11 of 13 with RuO4, (+)-spathulenol (6), (-)-allospathulenol (7), and the aromadendrane diols 8-11 could be prepared. Compounds 2-11 were tested for antifungal properties, but their activity was only moderate.