Helvetica Chimica Acta Vol. 86 (2003)
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successively diastereoisomers A (140 mg) and B (135mg) as colorless syrups of moderate purities which, after
crystallization in MeOH/H2O, afforded pure A (112 mg, 35%) and pure B (97 mg, 31%) as white crystals.
Data of Diastereoisomer A (9 or 9'): M.p. 119 1218. [a]2D5 À29.3 (c 1.1, CHCl3). 1H-NMR (CDCl3,
400 MHz): 0.03, 0.10, 0.15, 0.22 (4s, 2 Me2Si); 0.94, 0.96 (2s, 2 tBuSi); 1.00 1.23 (m 4 Me2CH); 2.40 2.60 (m, 4
Me2CH); 3.60 (ddd, 3J 9.8, 5.4, 1.7, HÀC(5')); 3.88 (dd, 3J 10, 7.2, HÀC(5)); 4.08 (dd, 2J 12, 3J
1.7, 1 HÀC(6')); 4.20 (m, HÀC(6), 1 HÀC(6')); 4.47 (br. d, 3J 7.2, HÀC(4)); 5.04 (−dd', 3J 9.8, 9.5,
HÀC(4')); 5.05 (−dd', 3J 9.5, 8.4, HÀC(2')); 5.15 (t, 3J 9.5, HÀC(3')); 5.25 (d, 3J 8.4, HÀC(1')); 5.55
(br. s, CCHCN); 5.91 (br. d, 3J 10, HÀC(2)); 6.59 (br. d, 3J 10, HÀC(3)). 13C-NMR (CDCl3 ,
100.57 MHz): À 4.94, À 4.19, À 4.05, À 3.61 (2 Me2Si); 17.92, 18.27, 18.74, 18.78, 18.88, 18.96, 18.98 (4 Me2CH,
2 Me3CSi); 25.75, 25.85 (2 Me3CSi); 33.80, 33.84 (4 Me2CH); 61.91 (C(6')); 68.25(C(4 ')); 71.06 (C(6)); 71.09
(C(2'); 72.21 (C(5')); 72.70 (C(3')); 75.20 C(4)); 80.79 (C(5)); 93.88 (CCHCN); 99.17 (C(1')); 116.69 (CN);
123.80 (C(3)); 137.46 (C(2)); 158.54 (C(1)); 175.24, 175.35, 176.04, 176.65 (4 CO).
Data of Diastereoisomer B (9 or 9'): M.p. 89 918. [a]2D5 21.9 (c 0.46, CHCl3). 1H-NMR (CDCl3,
400 MHz): 0.05, 0.09, 0.15, 0.25 (4s, 2 Me2Si); 0.8 1.2 (m, 2 tBuSi, 4 Me2CH); 2.38 2.57 (m, 4 Me2CH); 3.63
(ddd, 3J 9.7, 5.4, 2.1, HÀC(5')); 4.07 (dd, 3J 10.1, 7.4, HÀC(5)); 4.08 4.15 (m, CH2(6')); 4.28 (br. d, 3J 10.1,
HÀC(6)); 4.33 (br. d, 3J 7.4, HÀC(4)); 5.00 5.08 (m, HÀC(2'), HÀC(3'), HÀC(4')); 5.17 (d, 3J 8.1,
HÀC(1')); 5.38 (br. s, CCHCN); 5.96 (br. d, 3J 10.2, HÀC(2)); 6.54 (dd, 3J 10.2, 1.3, HÀC(3)). 13C-NMR
(CDCl3, 100.57 MHz): À 4.19, À 4.05(2 Me 2Si); 18.07, 18.10, 18.55, 18.67, 18.73, 18.85, 18.86, 19.37 (4 Me2CH, 2
Me3CSi); 25.75, 26.05 (2 Me3CSi); 33.70, 33.81, 33.84 (4 Me2CH); 61.97 (C(6')); 68.46 (C(4')); 71.73, 71.74 (C(4),
C(2')); 72.44 (C(5')); 72.72 (C(3')); 73.99 (C(6)); 79.11 C(5)); 93.16 (CCHCN); 98.52 (C(1')); 116.40 (CN);
123.14 (C(3)); 139.19 (C(2)); 159.00 (C(1)); 175.29, 175.36, 175.99, 176.58 (4 CO).
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