1974
Helvetica Chimica Acta – Vol. 91 (2008)
124.42 (¼CH); 124.28 (3 ¼CH); 124.06 (2 ¼CH); 123.48 (2 ¼CH); 118.50 (¼CH); 117.39 (¼CH); 63.50
(CH2O); 61.30 (SO2CH); 39.75 (6 ¼C(Me)CH2); 39.20 (¼C(Me)CH2); 37.54 (¼C(Me)CH2); 26.77 (3
¼CHCH2); 26.70 (3 ¼CHCH2); 26.45 (¼CHCH2); 26.26 (¼CHCH2); 25.70 (Me); 21.62 (MeÀAr);
21.02 (COMe); 17.68 (Me); 16.47 (7 Me); 16.42 (Me); 16.03 (Me). MALDI-MS: 917.7 ([M þ Na]þ,
C59H90NaO4Sþ).
(2E,6E,10E,14E,18E,22E,26E,30E,34E)-3,7,11,15,19,23,27,31,35,39-Decamethyltetraconta-2,6,10,
14,18,22,26,30,34,38-decaen-1-ol (21). To a stirred soln. of 19 (112 mg, 0.125 mmol) in MeOH (2 ml) and
Me2CO (3 ml), MeONa (2 mg, 0.034 mmol) was added, and the resulting mixture was stirred for 10 h at
r.t. to give deprotected product 20 in quant. yield. Without further purification, the residue was dissolved
in dry THF (10 ml) in the presence of [Pd(dppp)Cl2] (7.38 mg, 0.0125 mmol) at 08 under N2. LiHBEt3
(1.0m in THF, 0.25 ml, 0.25 mmol) was added dropwise over 10 min. The resulting mixture was allowed to
warm to r.t. over 3 h and then stirred for another 7 h. The reaction was quenched with 3m NaOH (1.5 ml)
and small amount of KCN and extracted with Et2O (3 Â 10 ml).The combined org. phase was washed
with H2O (3 Â 15 ml) and brine (10 ml), dried (MgSO4), and evaporated in vacuo. The crude product
was purified by CC (SiO2; PE/AcOEt 10 :1) to give 21 (71 mg, 81%). White solid. M.p. 41.9 – 42.78 from
MeOH (lit.: 42.5 – 43.58 [2b]). IR(film): 3330 (OH). 1H-NMR(CDCl 3): 5.43 (t, 3J ¼ 7.2, C¼CH); 5.11 –
5.14 (m, 9 C¼CH); 4.16 (d, 3J ¼ 6.8, CH2O); 2.14 – 1.99 (m, 18 CH2); 1.69 (s, 2 Me); 1.61 (s, 9 Me).
13C-NMR(CDCl 3): 139.85 (¼C); 135.42 (¼C); 135.03 (6 ¼C); 134.95 (¼C); 131.26 (¼C); 124.42 (2
¼CH); 124.27 (4 ¼CH); 124.17 (2 ¼CH); 123.77 (¼CH); 123.32 (¼CH); 59.42 (CH2O); 39.76
(¼C(Me)CH2); 39.58 (8 ¼C(Me)CH2); 26.78 (3 ¼CHCH2); 26.72 (3 ¼CHCH2); 26.68 (2 ¼CHCH2);
26.34 (¼CHCH2); 25.72 (Me); 17.70 (Me); 16.31 (Me); 16.04 (8 Me). ESI-MS: 722.0 (62, [M þ Na]þ),
609.6 (100), 535.6 (81).
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Received April 14, 2008