1
5.47 (2H, m, CH᎐CH). 13C-NMR: δ = 18.1 (CH -C᎐); 21.1
(Z)-2-Methyldec-8-ene-1,2-diol (5c). H-NMR: δ = 1.56 (3H,
s, CH3-Cquat.); 1.33–1.48 (8H, m, 4 × CH2); 1.60 (3H, d, J = 5.1,
CH -C᎐); 2.03 (2H, m, ᎐C–CH ); 3.40, 3.46 (1H each, dd, J = 11
᎐
᎐
3
(CH3-Cquat.); 25.3, 29.4, 29.7, 32.7, 37.0 (5 × CH2); 54.1
(CH2-O); 57.2 (Cquat.); 125.0, 131.7 (C᎐C). MS: 168.1502 [M]ϩ,
᎐
᎐
᎐
3
2
168.1514 (calc.).
and 5, CH -OH); 5.36–5.44 (2H, m, CH᎐CH). 13C-NMR:
᎐
2
δ = 13.0 (CH3-CH2); 23.4 (CH3-Cquat.); 23.9, 27.0, 29.7, 30.1, 39.0
2-Methyl-2-octyloxirane (7). Under an argon atmosphere,
a solution of trimethylsulfoxonium iodide (6.33 g, 28.8 mmol)
in dry DMSO (60 mL) was added slowly to a stirred suspension
of NaH (28.8 mmol) in anhydrous DMSO (12 mL)–THF
(18 mL) at 0 ЊC. After 30 min, decan-2-one (3.0 g, 19.2 mmol),
dissolved in dry DMSO (20 mL) was added dropwise. Then,
the cooling bath was removed and the reaction mixture was
stirred for 20 h at rt, after which semi-saturated NH4Cl solution
(150 mL) was added. The product was extracted with petroleum
ether and the combined organic phases were dried and evapor-
ated. Flash chromatography (petroleum ether–EtOAc, 20:1)
and Kugelrohr distillation gave pure 7; yield: 2.59 g (79%);
(5 × CH2); 70.0 (CH2-OH); 73.3 (Cquat.); 124.0, 130.9 (C᎐C).
᎐
1
(E)-2-Methyldec-4-ene-1,2-diol (6a). H-NMR: δ = 0.89 (3H,
t, J = 6.8, CH3-CH2); 1.16 (3H, s, CH3-Cquat.); 1.29–1.39 (6H,
m, (CH ) -CH ); 1.99–2.2 (6H, m, 2 CH -C᎐, 2 OH); 3.41, 2.47
᎐
2
3
3
2
(1H each, d, J = 11, CH -OH); 5.41–5.60 (2H, m, CH᎐CH).
᎐
2
13C-NMR: δ = 13.0 (CH3-CH2); 21.5, 22.6, 28.1, 30.4, 31.6, 41.0
(5 × CH2, CH3-Cquat.); 68.6 (CH2-OH); 71.5 (Cquat.); 123.3,
134.6 (C᎐C). (S)-6a: [α]20 Ϫ6.8 (c = 0.75, EtOH, 96% ee).
᎐
D
1
(E)-2-Methyldec-5-ene-1,2-diol (6b). H-NMR: δ = 0.85 (3H,
t, J = 7.0, CH3-CH2); 1.13 (3H, s, CH3-Cquat.); 1.23–1.32 (4H,
m, (CH2)2-CH3); 1.44–1.59 (2H, m, CH2-Cquat.); 1.92–2.12
(4H, m, 2 × ᎐C–CH ); 2.38, 2.65 (1H each, br s, OH); 3.36, 3.43
1
bp7 mbar (Kugelrohr): 130 ЊC. H-NMR: δ = 0.87 (3H, t, J = 6,
CH3-CH2); 1.22–1.66 (17H, m, 7 × CH2, CH3-Cquat.); 2.56, 2.60
(1H each, d, J = 4.9, CH2-O). 13C-NMR: δ = 14.1 (CH3-CH2);
20.9, 22.7, 25.3, 29.3, 29.6, 29.7, 31.9, 36.8 (7 × CH2, CH3-
Cquat.); 54.0 (CH2-O); 57.1 (Cquat.).
᎐
2
(1H each, dd, J = 11 and 5.8, CH2-OH); 5.33–5.47 (2H, m,
CH᎐CH). 13C-NMR: δ = 14.0 (CH3-CH2); 23.3 (CH3-Cquat.);
᎐
22.2, 27.0, 31.7, 32.3, 38.4 (5 × CH2); 69.8 (CH2-OH); 73.1
(Cquat.); 129.9, 130.0 (C᎐C).
᎐
Preparation of diols 4a–c, 5a–c, 6a–c and 8. Diols 4a–c, 5a–c,
6a–c and 8 were obtained by acid catalyzed hydrolysis of the
corresponding racemic oxiranes 1a–c, 2a–c, 3a–c and 7 [0.1 M
in H2O–THF (1:1) containing 3–10 drops of 12 M H2SO4].
Workup and flash chromatography (petroleum ether–EtOAc,
1:1) gave pure diols (55–90%). Their NMR data are listed below.
1
(E)-2-Methyldec-8-ene-1,2-diol (6c). H-NMR: δ = 1.12 (3H,
s, CH3-Cquat.); 1.29–1.44 (8H, m, 4 × CH2); 1.60 (3H, s, CH3-
C᎐); 1.94 (2H, s, ᎐C–CH ); 2.16 (1H, br s, OH); 2.43 (1H, br
᎐
᎐
2
s, OH); 3.36, 3.43 (1H each, d, J = 11, CH2-OH); 5.38 (2H, s,
CH᎐CH). 13C-NMR: δ = 17.9 (CH3-CH2); 23.2 (CH3-Cquat.);
᎐
23.7, 29.6, 29.8, 32.5, 38.8 (5 × CH2); 69.8 (CH2-OH); 73.1
1
(Cquat.); 124.8, 131.5 (C᎐C).
᎐
2-Methyldec-4-yne-1,2-diol (4a). H-NMR: δ = 0.90 (3H, t,
J = 7, CH3-CH2); 1.25 (3H, s, CH3-Cquat.); 1.25–1.57 (6H, m,
2-Methyldecane-1,2-diol (8). 1H-NMR: δ = 0.88 (3H,
t, J = 6.5, CH3-CH2); 1.16 (3H, s, CH3-Cquat.); 1.2–1.5 (14H, m,
7 × CH2); 3.47, 3.39 (1H each, d, J = 11, CH2-OH). 13C-NMR:
δ = 14.1 (CH3-CH2); 22.7, 23.3, 23.8, 29.3, 29.6, 30.3, 31.9,
38.8 (7 × CH2, CH3-Cquat.); 69.8 (CH2-OH); 73.1 (Cquat.). (S)-8:
[α]D20 Ϫ1.4 (c = 1.05, EtOH, 98% ee).
᎐
(CH ) -CH ); 2.06–2.52 (6H, m, CH -C᎐C-CH , 2 × OH); 3.48,
᎐
2
3
3
2
2
3.58 (1H each, dd, J = 11 and 5, CH2-OH). 13C-NMR: δ = 14.0
(CH3-CH2); 18.7, 22.2, 23.6, 28.7, 29.5, 31.1 (5 × CH2, CH3-
᎐
Cquat.); 69.1 (CH2-OH); 72.1 (Cquat.); 75.5, 84.0 (C᎐C).
᎐
2-Methyldec-5-yne-1,2-diol (4b). 1H-NMR: δ = 0.90 (3H,
t, J = 7.2, CH3-CH2); 1.19 (3H, s, CH3-Cquat.); 1.32–1.50 (4H,
m, (CH2)2-CH3); 1.65–1.83 (2H, m, CH2-CH2-Cquat.); 2.12–
Preparation of monomethylated derivatives 17 and 18. Mono-
methylated derivatives 17 and 18 were obtained either from the
corresponding epoxide by refluxing them in NaOMe–MeOH-
solution or from the corresponding diol by treatment with
KOH–MeI in DMSO via standard procedures. Methylation was
closely monitored via TLC, since prolonged reaction times led
to partial dimethylation. NMR data of these compounds are
given below.
᎐
᎐
2.16 (2H, m, CH C᎐); 2.27–2.30 (3H, m, CH -C᎐, OH);
᎐
᎐
2
2
2.59 (1H, br s, OH); 3.43, 3.51 (1H each, d, J = 11, CH2-OH).
13C-NMR: δ = 13.5 (CH3-CH2); 23.3 (CH3-Cquat.); 13.6, 18.4,
22.0, 31.1, 37.3 (5 × CH2); 69.8 (CH2-OH); 72.9 (Cquat.); 80.0,
᎐
81.4 (C᎐C).
᎐
2-Methyldec-8-yne-1,2-diol (4c). 1H-NMR: δ = 1.12 (3H,
s, CH3-Cquat.); 1.22–1.48 (8H, m, 4 × CH2); 1.74 (3H, br s,
1-Methoxy-2-methyldec-4-yn-2-ol (17). 1H-NMR: δ = 0.89
(3H, t, J = 7, CH3-CH2); 1.24 (3H, s, CH3-Cquat.); 1.27–1.52
᎐
᎐
CH -C᎐); 2.03–2.17 (2H, br s, CH -C᎐); 2.24, 2.52 (1H each,
᎐
᎐
3
2
br s, OH); 3.36, 3.42 (1H each, dd, J = 11 and 6, CH2-OH).
᎐
(6H, m, 3 × CH ); 2.1–2.2 (2H, m, CH -CH -C᎐); 2.38 (2H,
13
᎐
2
2
2
᎐
C-NMR: δ = 3.5 (CH -C᎐); 23.2 (CH -Cquat.); 18.7, 23.4,
᎐
3
3
᎐
t, J = 2.4, Cquat.-CH -C᎐); 2.44 (1H, s, OH); 3.26, 3.38 (1H each,
᎐
2
29.0, 29.5, 38.6 (5 × CH2); 69.8 (CH2-OH); 73.1 (Cquat.); 75.6,
d, J = 9, CH2-O-CH3); 3.39 (3H, s, CH2-O-CH3). 13C-NMR:
᎐
79.3 (C᎐C).
᎐
δ = 14.0 (CH3-CH2); 18.7, 22.2, 23.6, 28.7, 29.8, 31.1 (5 × CH2,
᎐
CH3-Cquat.); 59.4 (CH2-O-CH3); 71.6 (Cquat.); 76.0, 83.0 (C᎐C);
(Z)-2-Methyldec-4-ene-1,2-diol (5a). 1H-NMR: δ = 0.88 (3H,
t, J = 6.6, CH3-CH2); 1.16 (3H, s, CH3-Cquat.); 1.22–1.38 (6H, m,
᎐
78.5 (CH2-O-CH3).
(CH ) -CH ); 1.99–2.37 (5H, m, 2 × CH -C᎐, OH); 3.40, 2.48
᎐
2
3
3
2
1
1-Methoxy-2-methyldecan-2-ol (18). H-NMR: δ = 0.87 (3H,
(1H each, d, J = 11, CH -OH); 5.36–5.64 (2H, m, CH᎐CH).
᎐
2
t, CH3-CH2); 1.34 (3H, s, CH3-Cquat.); 1.23–1.52 (14H, m,
7 × CH2); 2.17 (1H, s, OH); 3.18, 3.25 (1H each, d, J = 9, CH2-
O-CH3); 3.38 (3H, s, CH2-O-CH3). 13C-NMR: δ = 14.1 (CH3-
CH2); 23.7 (CH3-Cquat.); 22.7, 23.8, 29.3, 29.6, 30.3, 31.9
(6 × CH2); 39.2 (CH2-CH2-Cquat.); 59.3 (CH2-O-CH3); 72.1
(Cquat.); 80.0 (CH3-O-CH2).
13C-NMR: δ = 14.1 (CH3-CH2); 22.6, 23.5, 27.4, 29.3, 31.6, 36.3
(5 × CH2, CH3-Cquat.); 69.6 (CH2-OH); 73.1 (Cquat.); 123.5,
134.1 (C᎐C).
᎐
(Z)-2-Methyldec-5-ene-1,2-diol (5b). 1H-NMR: δ = 0.87 (3H,
t, J = 6.7, CH3-CH2); 1.16 (3H, s, CH3-Cquat.); 1.24–1.32 (4H,
m, (CH2)2-CH3); 1.44–1.59 (2H, m, CH2-Cquat.); 1.99–2.12 (5H,
General procedure for the biocatalytic hydrolysis of epoxides
m, 2 × ᎐C-CH , OH); 2.23 (1H, br s, OH); 3.39, 3.45 (1H each,
᎐
2
dd, J = 11 and 5.6, CH -OH); 5.30–5.40 (2H, m, CH᎐CH).
Lyophilized microbial cells (45–50 mg) were rehydrated in Tris-
buffer (1 mL, 0.05 M, pH 8.0) for ca. 1 hour in an Eppendorf
vial on a rotary shaker (130 rpm, rt). Substrate (5 µL) was
then added and the mixture was shaken at 30 ЊC with 130 rpm.
᎐
2
13C-NMR: δ = 14.0 (CH3-CH2); 23.3 (CH3-Cquat.); 21.7, 21.8,
22.4, 27.0, 38.5 (5 × CH2); 69.8 (CH2-OH); 73.1 (Cquat.); 129.3,
130.6 (C᎐C).
᎐
3784
J. Chem. Soc., Perkin Trans. 1, 2000, 3779–3785