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3.12 (m, 3H, H-2, CH2NH), 2.83 (t, 1H, Jgem¼Jvic¼4.8, H-3a), 2.64 (dd,
1H, Jvic¼2.4, H-3b), 1.50–1.46 (m, 2H, CH2-decyl), 1.25–1.20 (m, 14H,
(CHal), 1693 (CO). ESI-HRMS calcd for C9H15NO3Na: 208.0950.
Found: 208.0949 [MþNa]þ.
CH2-decyl), 0.87 (m, 3H, CH3). 13C NMR (75 MHz, CDCl3)
d 156.0
(CO), 65.4 (C-1), 49.8 (C-2), 44.6 (C-3), 41.1 (CH2NH), 35.4 (CH2),
31.8, 29.9, 29.5, 29.2, 26.7, 22.6 (CH2-decyl), 14.1 (CH3). MS (APCIþ):
m/z 258.6 [MþH]þ. IR (KBr) 2955, 2917, 2848 (CH), 1686 (CO), 1565
(NHCO). Anal. Calcd for C14H27NO3 (257.37): C, 65.33; H, 10.57; N,
5.44. Found: C, 65.05; H, 10.58; N, 5.42.
4.5.7. Glycidyl N-(4-benzyl)piperazinyl carbamate 10g. Compound
10g was isolated (eluent: Hex/EA 2/3) in 69% yield as a colorless oil.
1H NMR (400 MHz, CDCl3)
d 7.31–7.20 (m, 5H, H–Ar), 4.40 (dd, 1H,
Jgem¼12.0, Jvic¼2.8, H-1a), 3.86 (dd, 1H, Jvic¼6.4, H-1b), 3.46 (m, 6H,
CH2N, CH2Ph), 3.18 (m, 1H, H-2), 2.79 (t, 1H, Jgem¼Jvic¼4.8, H-3a),
2.59 (dd, 1H, Jvic¼2.8, H-3b), 2.38 (br s, 4H, CH2N). 13C NMR
4.5.2. Glycidyl N-dodecylcarbamate 10b. Compound 10b was iso-
(100 MHz, CDCl3) d 154.7 (CO), 137.6 (CIV–Ar), 129.0, 128.2, 127.1
lated (eluent: Hex/EA 4/1) in 83% yield as a white solid, mp 50–
(CH–Ar), 65.8 (C-1), 62.9 (CH2Ph), 52.5, 43.7 (CH2N), 49.7 (C-2), 44.4
(C-3). MS (IS): m/z 277.0 [MþH]þ, 299.0 [MþNa]þ. IR (neat) 2942,
2809 (CH), 1697 (CO). ESI-HRMS calcd for C15H21N2O3: 277.1552.
Found: 277.1539 [MþH]þ.
52 ꢁC (CH2Cl2). 1H NMR (300 MHz, CDCl3)
d 4.79 (br s, 1H, NH), 4.42
(dd, 1H, Jgem¼12.3, Jvic¼3.0, H-1a), 3.86 (dd, 1H, Jvic¼6.6, H-1b),
3.22–3.12 (m, 3H, H-2, CH2NH), 2.83 (t,1H, Jgem¼Jvic¼4.8, H-3a), 2.63
(dd, 1H, Jvic¼2.7, H-3b), 1.50–1.45 (m, 2H, CH2-dodecyl), 1.32–1.20
(m, 18H, CH2-dodecyl), 0.87 (m, 3H, CH3). 13C NMR (75 MHz, CDCl3)
4.6. Standard procedure for the synthesis of 11a–d
d
156.0 (CO), 65.2 (C-1), 49.8 (C-2), 44.6 (C-3), 41.1 (CH2NH), 31.9,
29.9, 29.6, 29.5, 29.3, 26.7, 22.7 (CH2-dodecyl), 14.1 (CH3). MS
(APCIþ): m/z 286.6 [MþH]þ. IR (KBr) 2955, 2917, 2848 (CHal), 1686
(CO), 1565 (NHCO). Anal. Calcd for C16H31NO3 (285.43): C, 67.33; H,
10.95; N, 4.91. Found: C, 67.75; H, 11.16; N, 5.21.
To a solution of tosylated GC 2 (0.272 g, 1 mmol) in DMF (2 mL)
cooled at 0 ꢁC, were added potassium carbonate (0.166 g, 1.2 equiv)
and the appropriate thiol (1.2 equiv). The reaction mixture was
heated at 80 ꢁC for 4 h. After dilution with ethyl acetate and water,
the organic layer was washed with water, brine, then dried over
MgSO4. After filtration and concentration of the solution in vacuo,
the residue was purified by flash column chromatography (eluent:
PE/EA).
4.5.3. Glycidyl N-allylcarbamate 10c. Compound 10c was isolated
(eluent: Hex/EA 3/2) in 64% yield as a colorless oil. 1H NMR
(400 MHz, CDCl3)
d 5.89–5.80 (m, 1H, ]CH), 5.23–5.11 (m, 2H,
]CH2), 5.03 (br s, 1H, NH), 4.45 (dd, 1H, Jgem¼12.4, Jvic¼2.8, H-
1a), 3.86 (dd, 1H, Jvic¼6.4, H-1b), 3.81 (t, 2H, Jvic¼5.6, CH2NH),
3.21 (m, 1H, H-2), 2.84 (t, 1H, Jgem¼Jvic¼4.8, H-3a), 2.64 (dd, 1H,
4.6.1. 4-(n-Hexylsulfanyl)methyl-1,3-dioxolan-2-one 11a. Compo-
und 11a was isolated (eluent: Hex/EA 9/1) in 84% yield as a col-
Jvic¼2.4, H-3b). 13C NMR (100 MHz, CDCl3)
d
155.9 (CO), 134.2
orless oil. 1H NMR (400 MHz, CDCl3)
d 4.83 (m, 1H, H-4), 4.57 (t,
(]CH), 116.0 (]CH2), 65.4 (C-1), 49.7 (C-2), 44.5 (C-3), 43.4
(CH2NH). MS (APCIþ): m/z 158.3 [MþH]þ. IR (NaCl) 3068, 3006,
2929 (C), 1711 (CO), 1531 (NHCO), 1245 (C–O–C). Anal. Calcd for
C7H11NO3 (157.17): C, 53.49; H, 7.05; N, 8.91. Found: C, 52.89; H,
7.15; N, 8.90.
1H, Jgem¼Jvic¼8.4, H-5a), 4.29 (dd, 1H, Jvic¼6.4, H-5b), 2.92 (dd, 1H,
Jgem¼14.0, Jvic¼4.8, SCHa), 2.79 (dd, 1H, Jvic¼8.0, SCHb), 2.62–2.58
(m, 2H, SCH2-hexyl), 1.62–1.55 (m, 2H), 1.42–1.23 (m, 6H, CH2-
hexyl), 0.89 (t, 3H, Jvic¼8.6, CH3). 13C NMR (100 MHz, CDCl3)
d
154.5 (CO), 75.5 (C-4), 68.6 (C-5), 34.6 (SCH2), 33.0 (SCH2-hexyl),
31.3, 29.5, 28.3, 22.4 (CH2-hexyl), 13.9 (CH3). MS (IS): m/z 219.0
[MþH]þ, 241.0 [MþNa]þ. IR (NaCl) 3019 (CH), 1806 (CO). ESI-
HRMS calcd for C10H18O3SNa: 241.0874. Found: 241.0883
[MþNa]þ.
4.5.4. Glycidyl N-benzylcarbamate 10d [170956-42-0]22b. Compound
10d was isolated (eluent: Hex/EA 7/3) in 80% yield as a colorless oil.
1H NMR (300 MHz, CDCl3)
d 7.38–7.26 (m, 5H, H–Ar), 5.13 (br s, 1H,
NH), 4.48 (dd, 1H, Jgem¼12.3, Jvic¼3.0, H-1a), 4.39 (d, 2H, Jvic¼6.0,
CH2NH), 3.92 (dd, 1H, Jvic¼6.3, H-1b), 3.22 (m, 1H, H-2), 2.85 (t, 1H,
Jgem¼Jvic¼4.8, H-3a), 2.65 (dd, 1H, Jvic¼2.4, H-3b). 13C NMR (75 MHz,
4.6.2. 4-(Benzylsulfanyl)methyl-1,3-dioxolan-2-one 11b. Compound
11b was isolated (eluent: Hex/EA 9/1) in 38% yield as a colorless
CDCl3)
d
156.0 (CO), 138.2 (CIV–Ar), 128.6, 127.5 (CH–Ar), 65.5 (C-1),
oil. 1H NMR (400 MHz, CDCl3)
d 7.37–7.27 (m, 5H, H–Ar), 4.67 (m,
49.7 (C-2), 45.1 (CH2NH), 44.6 (C-3). MS (APCIþ): m/z 208.4 [MþH]þ.
IR (NaCl) 3063, 3031, 2943 (CHAr), 1706 (CO), 1534 (NHCO), 1256 (C–
O–C). Anal. Calcd for C11H13NO3 (207.23): C, 63.76; H, 6.32; N, 6.76.
Found: C, 63.62; H, 6.44; N, 6.57.
1H, H-4), 4.44 (t, 1H, Jgem¼Jvic¼8.4, H-5a), 4.16 (dd, 1H, Jvic¼6.6, H-
1b), 3.81 and 3.77 (2d, AB system, 2H, Jgem¼13.7, PhCH2), 2.79 (dd,
1H, Jgem¼14.3, Jvic¼4.7, SCHa), 2.68 (dd, 1H, Jvic¼7.3, SCHb). 13C
NMR (100 MHz, CDCl3)
d 154.5 (CO), 137.3 (CIV–Ar), 128.9, 128.8,
127.6 (CH–Ar), 75.4 (C-4), 68.5 (C-5), 36.8 (PhCH2), 33.4 (SCH2). MS
(IS): m/z 247.4 [MþNa]þ. IR (NaCl) 1793 (CO), 1167, 1064 (CH). ESI-
HRMS calcd for C11H12O3SNa: 247.0405. Found: 247.0395
[MþNa]þ.
4.5.5. GlycidylN-morpholinylcarbamate 10e [117382-54-4]. Compound
10e was isolated (eluent: Hex/EA 2/3) in 53% yield as a colorless oil. 1H
NMR (400 MHz, CDCl3)
d
4.47 (dd, 1H, Jgem¼12.0, Jvic¼2.8,, H-1a), 3.91
(dd, 1H, Jvic¼6.4, H-1b), 3.65 (m, 4H, CH2O-morph), 3.49 (m, 4H, CH2N-
morph), 3.23 (m, 1H, H-2), 2.85 (t, 1H, Jgem¼Jvic¼5.0, H-3a), 2.63 (dd,
4.6.3. 4-(Cyclopentylsulfanyl)methyl-1,3-dioxolan-2-one 11c. Com-
pound 11c was isolated (eluent: Hex/EA 9/1) in 68% yield as a col-
1H, Jvic¼2.8, H-3b). 13C NMR (100 MHz, CDCl3)
d 154.9 (CO), 66.5
(CH2O), 66.2 (C-1), 49.7 (C-2), 44.5 (C-3), 44.1, 44.0 (CH2N). MS (IS): m/z
188.0 [MþH]þ, 210.0 [MþNa]þ. IR (neat) 2972, 2923, 2867 (CH), 1694
(CO), 1534 (NHCO), 1256 (C–O–C). ESI-HRMS calcd for C8H13NO4Na:
210.0742. Found: 210.0748 [MþNa]þ.
orless oil. 1H NMR (400 MHz, CDCl3)
d 4.84 (m, 1H, H-4), 4.56 (t, 1H,
Jgem¼Jvic¼8.8, H-5a), 4.28 (dd, 1H, Jvic¼6.8, H-5b), 3.20–3.13 (m, 1H,
CHS), 2.96 (dd, 1H, Jgem¼14.0, Jvic¼4.8, SCHa), 2.79 (dd, 1H, Jvic¼8.0,
SCHb), 2.04–1.97 (m, 2H), 1.80–1.68 (m, 2H), 1.64–1.43 (m, 4H, CH2-
cyclopentyl), 1.64–1.43 (m, 4H, CH2). 13C NMR (100 MHz, CDCl3)
4.5.6. Glycidyl N-piperidinylcarbamate 10f [96426-72-1]. Compound
10f was isolated (eluent: Hex/EA 2/3) in 61% yield as a colorless oil.
d 154.6 (CO), 75.4 (C-4), 68.7 (C-5), 44.5 (CHS), 34.4 (SCH2), 33.99
(CH2), 33.80 (CH2), 24.7, 24.6 (CH2-cyclopentyl). MS (IS): m/z 203.0
1H NMR (400 MHz, CDCl3)
d
4.43 (dd, 1H, Jgem¼12.4, Jvic¼3.2, H-1a),
[MþH]þ, 225.0 [MþNa]þ. IR (neat) 2954 (CHal), 1790 (CO).
3.91 (dd, 1H, Jvic¼6.4, H-1b), 3.43 (m, 4H, CH2N), 3.23 (m, 1H, H-2),
2.84 (t, 1H, Jgem¼Jvic¼4.8, H-3a), 2.63 (dd, 1H, Jvic¼2.8, H-3b), 1.62–
4.6.4. 4-(6-Hydroxyhexylsulfanyl)methyl-1,3-dioxolan-2-one11d. Com-
pound 11d was isolated (eluent: PE/EA 3/2) in 39% yield as a col-
1.54 (m, 6H, CH2-pip). 13C NMR (100 MHz, CDCl3)
d 155.0 (CO), 65.7
(C-1), 49.9 (C-2), 44.9 (CH2N), 44.6 (C-3), 25.6, 25.5, 24.3 (CH2-pip).
orless oil. 1H NMR (400 MHz, CDCl3)
d
4.84 (m, 1H, H-4), 4.54 (t,
MS (IS) m/z 186.0 [MþH]þ, 208.0 [MþNa]þ. IR (neat) 2935, 2856
1H, Jgem¼Jvic¼8.4, H-5a), 4.25 (dd, 1H, Jvic¼6.4, H-5b), 3.58 (t, 2H,