2046
R. S. Ferrarini et al. / Tetrahedron: Asymmetry 20 (2009) 2043–2047
Low resolution mass spectra were obtained on a Shimadzu CG 17A/
CG/MS-QP5050A instrument. Near IR spectra were obtained on a
Bomen MB-100 spectrometer. Elemental analyses were performed
at the Microanalytical Laboratory of the Institute of Chemistry,
Universidade de São Paulo. IUPAC names were obtained using
the software ChemDraw, version 8.0.
e.e. 100%); lit.21
½
a 2D1
ꢃ
¼ þ0:9 (c 2.04 CHCl3; reported e.e. 95.5%);
found ½a 2D2
ꢃ
¼ þ0:95 (c 1.02, CHCl3, 99% e.e.).
(S,E)-Tridec-10-en-2-ol 5: (yield 76%); colorless oil: dH (500 MHz,
CDCl3) 0.96 (t, J = 7.5 Hz, 3H); 1.19 (d, J = 6.0 Hz, 3H); 1.29–1.47 (m,
12H); 1.95–2.02 (m, 4 H); 3.79 (sext, J = 6.0 Hz, 1H); 5.37–5.47 (m,
2H); dC (125 MHz, CDCl3) 13.9; 23.5; 25.6; 25.8; 29.1; 29.5; 29.6;
29.7; 32.5; 39.4; 68.2; 129.3; 131.9; MS m/z (rel int.) 198 (M+, 2);
180 (4) 151 (2); 138 (6); 109 (16); 95 (42); 82 (78); 68 (100); 55
(70); 41 (92); IR cmꢀ1 (neat) 3361; 2963; 2927; 2854; 1461;
4.3. Typical procedures
4.3.1. Preparation of higher order cyanocuprate from
hydroxytelluride (S)-8 and its reaction with tosylates
1374; 965; lit.21
½
a 2D2
ꢃ
¼ þ6:4 (c 8.89 CHCl3; reported e.e. 95.5%);
found ½a 2D0
ꢃ
¼ þ6:8 (c 1.00 CHCl3).
To a 25 mL two-necked round-bottomed flask equipped with
magnetic stirring under a nitrogen atmosphere containing a THF
(8 mL) solution of hydroxytelluride (S)-8 (1.03 g, 4 mmol) at
Acknowledgments
ꢀ70 °C was slowly added n-butyllithium (2 equiv, 1.9 mol Lꢀ1
,
The authors wish to thank FAPESP, CAPES, and CNPq for finan-
cial support. Novozymes Inc. is acknowledged for the generous gift
of lipase.
4.2 mL, 8 mmol, solution in hexane). The resulting clear solution
was stirred for 40 min. To a second two-necked round-bottomed
flask equipped with magnetic stirring under a nitrogen atmosphere
were added CuCN (179 mg, 2 mmol) and THF (6 mL). The light yel-
low solution of the first flask was transferred via a cannula to the
second flask, and the temperature was maintained at ꢀ70 °C for
20 min. To the resulting clear yellow solution was added a THF
(1 mL) solution of the appropriate tosylate (1 mmol). The reaction
was monitored by TLC until total consumption of the tosylate was
observed (about 6 h). The reaction media was warmed to room
temperature and quenched with an ammonium chloride/ammo-
nium hydroxide solution (3:1, 4 mL) and vigorously stirred. The
aqueous and organic phases were separated and the aqueous phase
was washed with ethyl acetate (3 ꢂ 10 mL). The organic phases
were combined and washed with brine (1 ꢂ 5 mL), dried over mag-
nesium sulfate, and filtered. Evaporation of the solvents gave the
crude product, which was purified by silica gel flash chromatogra-
phy eluting with hexane/ethyl acetate. Acetates 3, (S)-3, (S)-4, and
(S,S)-2 were obtained directly by quenching the reaction media
with acetic anhydride or by diluting the crude extracted product
in pyridine (4 mL) at 0 °C followed by the addition of acetic anhy-
dride (2.5 mmol for acetates 3, (S)-3, (S)-4, and 5 mmol for diace-
tate (S,S)-2.
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(2S,12S)-Tridecane-2,12-diyl diacetate (S,S)-2: (yield 64%); color-
less oil: dH (500 MHz, CDCl3) 1.20 (d, J = 6.5 Hz, 6H); 1.26–1.34 (m,
14H); 1.43–1.48 (m, 2H); 1.54–1.61 (m, 2H); 2.02 (s, 6H); 4.88
(sext, J = 6.5 Hz, 2H); dC (125 MHz, CDCl3) 19.9; 21.4; 25.4; 29.4;
29.5; 29.6; 35.9; 71.1; 170.8; MS m/z (rel int.) 300 (M+, <1); 257
(3); 197 (1); 180 (5); 138 (5); 110 (2); 96 (15); 87 (10); 68 (2);
55 (4); 43 (100); IR cmꢀ1 (neat) 2930; 2857; 1738; 1372; 1244;
1127; 1023; lit.15
(c 1.20 CHCl3);
½
a 2D3
ꢃ
¼ þ1:8 (c 1,21 CHCl3), found ½a D20
¼ þ2:0
ꢃ
(2S)-Tridec-2-yl acetate (S)-3: (yield 80%); colorless oil: dH
(300 MHz, CDCl3) 0,88 (t, J = 6.3 Hz, 3H); 1.19 (d, J = 6.3 Hz, 3H);
1.26–1.60 (m, 20H); 2.02 (s, 3H); 4.88 (sext, J = 6.3 Hz, 1H); dC
(75 MHz, CDCl3) 14.1; 19.9; 21.3; 22.7; 25.4; 29.3; 29.4; 29.5;
29.55; 29.6; 31.9; 35.9; 71.0; 170.7; MS m/z (rel int.) 207 (1);
182 (8); 111 (8); 97 (16); 87 (21); 83 (15); 71 (10); 69 (20); 57
(20); 43 (100); IR cmꢀ1 (neat) 2926; 2855; 1734; 1464; 1372;
1244; 1022; lit.5
½
a 3D1
ꢃ
¼ þ0:8 (c 0.8 CHCl3); lit.16
½
a 2D3
ꢃ
¼ þ4:3
(c = 0.95 hexane; reported e.e. 93.5%); lit.17
½
a 1D8
ꢃ
¼ þ4:5 (c 0.98
hexane; reported e.e. 98%); lit.18
½
a 2D1
ꢃ
¼ þ2:1 (c 0.25 hexane);
lit.19
½
a 23
ꢃ
¼ þ3:4 (c 0.94 hexane; reported e.e. 90%); found
½
a 2D0
ꢃ
¼ þD4:5 (c 1.00 hexane). The analytical data of racemic 3 are
identical to those of (S)-3.
(S,E)-Tridec-10-en-2-yl acetate (S)-4: (yield 93%); colorless oil:
dH (200 MHz, CDCl3) 0.96 (t, J = 7.46 Hz, 3H); 1.19 (d, J = 6.6 Hz,
3H); 1.27–1.42 (m, 12H); 1.92–1.98 (m, 4 H); 2.02 (s, 3H); 4.88
(sext, J = 6.1 Hz, 1H); 5.29–5.51 (m, 2H); dH (50 MHz, CDCl3) 13.9;
19.9; 21.4; 25.4; 25.6; 29.0; 29.4; 29.6; 29.7; 32.5; 35.9; 71.1;
129.3; 131.9; 170.8; lit.20
½
a 2D5
ꢃ
¼ þ4:3 (c 2.42 pentane; reported