8120 J . Org. Chem., Vol. 62, No. 23, 1997
Dondoni et al.
4.09 (dd, 1H, H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0 Hz), 4.11-4.12 (m,
2H, H-13, H-13′), 4.17 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 2.0
Hz), 4.37 (ddd, 1H, H-8, J 8,6 ) 1.0 Hz, J 8,7 ) 6.5 Hz, J 8,9 ) 4.0
Hz), 4.40 (dd, 1H, H-9, J 9,10 ) 6.0 Hz), 4.48 (dd, 1H, H-10),
4.53 (dd, 1H, H-3), 4.63 (dt, H-12, J 12,13 ≈ J 12,13′ ≈ 6.0 Hz),
4.82 (dd, 1H, H-5, J 5,6 ) 6.4 Hz), 5.56 (d, 1H, H-1), 5.98 (ddd,
1H, H-7, J 7,5 ) 1.0 Hz, J 7,6 ) 12.0 Hz), 6.06 (ddd, 1H, H-6);
13C NMR δ 24.3, 24.7, 24.9, 25.2, 25.8, 25.9, 26.3, 27.0, 65.1,
67.2, 70.2, 70.8, 72.9, 73.4, 78.8, 80.8, 81.9, 82.7, 96.4, 108.4,
75.3, 75.6, 76.7, 77.7, 79.8, 85.0, 97.1, 108.5, 109.0, 127.2, 128.7,
127.7-128.7, 138.8, 139.1, 139.2, 139.4. Anal. Calcd for
C47H54O10: C, 72.47, H, 6.99. Found: C, 71.73, H, 7.20.
Eluted second was (E)-12 as a syrup: [R]D ) -47 (c 0.4); 1H
NMR δ 1.26, 1.30, 1.35, 1.45 (4 × s, 12H, 2 × C(CH3)2), 3.42
(ddd, 1H, H-12, J 12,11 ) 10.0 Hz, J 12,13 ) 5.0 Hz, J 12,13′ ) 2.0
Hz), 3.63 (dd, 1H, H-10, J 10,9 ) 3.0 Hz, J 10,11 ) 10.0 Hz), 3.76
(m, 2H, H-13, H-13′), 3.83 (d, 1H, H-9), 3.94 (d, 1H, H-8, J 8,7
) 5.0 Hz), 3.95 (t, 1H, H-11), 4.22 (dd, 1H, H-4, J 4,3 ) 8.0 Hz,
J 4,5 ) 2.0 Hz), 4.32 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 3.0 Hz),
4.34 (d, 1H, H-5, J 5,6 ) 5.0 Hz), 4.56 and 4.89 (2 × d, 2H, J )
10.0 Hz, OCH2Ph), 4.57 and 4.66 (2 × d, 2H, J ) 12.0 Hz,
OCH2Ph), 4.61 (dd, 1H, H-3), 4.62 and 4.65 (2 × d, 2H, J )
12.0 Hz, OCH2Ph), 4.78 and 4.85 (2 × d, H, J ) 12.0 Hz, OCH2-
Ph), 5.59 (d, 1H, H-1), 5.91 (dd, 1H, H-6, J 6,7 ) 16.0 Hz), 6.00
(dd, 1H, H-7), 7.05-7.40 (m, 20H, Harom); 13C NMR (C6D6) δ
24.3, 24.9, 26.3, 69.0, 70.3, 71.0, 71.3, 71.9, 73.7, 73.8, 75.1,
75.2, 75.5, 77.6, 78.9, 80.2, 85.0, 97.0, 108.3, 109.1, 127.2, 131.7,
109.2, 109.3, 112.6, 127.5, 128.9. Anal. Calcd for C25H38O10
:
C, 60.23; H, 7.68. Found: C, 59.74, H, 7.67.
1
Eluted second was (E)-11 as an oil: [R]D ) -36 (c 0.2); H
NMR (C6D6) δ 1.13, 1.15, 1.16, 1.32, 1.40, 1.48, 1.50 (7 × s,
24H, 4 × C(CH3)2), 3.32 (dd, 1H, H-11, J 11,10 ) 3.5 Hz, J 11,12
)
7.0 Hz), 3.60 (dd, 1H, H-8, J 8,7 ) 6.0 Hz, J 8,9 ) 4.0 Hz), 3.91
(dd, 1H, H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0 Hz), 4.02 (dd, 1H, H-9,
J 9,10 ) 6.0 Hz), 4.05 (dd, 1H, H-13, J 13,12 ) 6.0 Hz, J 13,13′ ) 8.0
Hz), 4.14 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 2.0 Hz), 4.18 (dd,
H-13′, J 13′,12 ) 5.7 Hz, J 13′,13 ) 8.0 Hz), 4.26 (dd, 1H, H-10),
4.43 (dd, 1H, H-3), 4.52 (dd, 1H, H-5, J 5,6 ) 5.7 Hz), 4.56 (dt,
1H, H-12), 6.24 (2H, H-6, H-7, J 6,7 ) 15.3 Hz, J 8,7 ) 6.0 Hz);
13C NMR δ 24.3, 24.6, 24.9, 25.1, 25.8, 26.0, 26.1, 27.0, 67.1,
68.5, 70.3, 70.8, 73.1, 73.3, 76.0, 80.8, 81.8, 82.5, 96.4 108.5,
127.5-128.3, 139.3, 139.7. Anal. Calcd for C47H54O10
72.47, H, 6.99. Found: C, 72.07, H, 7.44.
: C,
(Z)-8,12-An h yd r o-9-a zid o-10,11,13-t r i-O-b en zyl-6,7,9-
tr ideoxy-1,2:3,4-di-O-isopr opyliden e-r-D-glycer o-L-ma n n o-
D-ga la cto-tr id ec-6-en o-1,5-p yr a n ose (13). The phosphoni-
um salt 8 (209 mg; 0.33 mmol) was reacted with the aldehyde
4 (161 mg; 0.33 mmol) as described for the preparation of 10
to afford, after flash chromatography (4:1 cyclohexane-ethyl
acetate), 192 mg (80%) of the olefin 13, exclusively in the form
of the Z-isomer, as a syrup: [R]D ) -20 (c 0.5); 1H NMR (C6D6)
δ 1.07, 1.15, 1.50, 1.55 (4 × s, 12H, 2 × C(CH3)2), 3.32 (dd,
1H, H-10, J 10,9 ) 10.0 Hz, J 10,11 ) 3.0 Hz), 3.49 (dd, 1H, H-13′,
109.2, 112.5, 127.6, 131.5. Anal. Calcd for C25H38O10
60.23; H, 7.68. Found: C, 60.49; H, 7.42.
: C,
(Z/E)-8,12-An h yd r o-9,10,11,13-t et r a -O-b en zyl-6,7-d i-
d eoxy-1,2:3,4-d i-O-isop r op ylid en e-r-D-glycer o-D-ga la cto-
D-ga la cto-tr id ec-6-en o-1,5-p yr a n ose (12). The phospho-
nium salt 8 (330 mg; 0.52 mmol) was reacted with the aldehyde
3 (287 mg; 0.52 mmol) as described for the preparation of 10.
Flash chromatography (5:1 cyclohexane-ethyl acetate) of the
residue gave first a 1:2 mixture of (E)-32 and (Z)-32 (70 mg,
20%). Flash chromatography (30:1 toluene-acetone) afforded
almost pure samples of these isomers. (Z)-32: 1H NMR (C6D6)
δ 1.10, 1.15, 1.50, 1.55 (4 × s, 12H, 2 × C(CH3)2), 3.65 (dd,
1H, H-13, J 13,12 ) 7.5 Hz, J 13,13′ ) 10.0 Hz), 3.77 (dd, 1H, H-11,
J 13′,12 ) 5.0 Hz, J 13′,13 ) 8.0 Hz), 3.58 (dd, 1H, H-12, J 12,13
)
8.0 Hz), 3.74 (t, 1H, H-13), 3.88 (t, 1H, H-9, J 9,8 ) 10.0 Hz),
3.92 (1H, H-11), 4.14-4.26 (m, 4H, H-8, H-2, OCH2Ph), 4.29
(dd, 1H, H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0 Hz), 4.32 and 4.38 (2d,
2H, J ) 12.0 Hz, OCH2Ph), 4.96 (dd, 1H, H-5, J 5,6 ) 8.0 Hz),
5.55 (d, 1H, H-1, J 2,1 ) 5.0 Hz), 5.64 (ddd, 1H, H-7, J 7,5 ) 1.0
J 11,12 ) 9.0 Hz, J 11,10 ) 6.5 Hz), 3.92 (dd, 1H, H-13′, J 13′,12
)
Hz, J 7,6 ) 11.0 Hz, J 7,8 ) 8.0 Hz), 6.18 (ddd, 1H, H-6, J 6,8
)
2.5 Hz), 4.15 (ddd, 1H, H-12), 4.21 (m, 2H, H-2, H-10), 4.25
and 4.50 (2 × d, 2H, J ) 12.0 Hz, OCH2Ph), 4.34 and 4.41 (2
× d, 2H, J ) 12.0 Hz, OCH2Ph), 4.40 (m, 1H, H-3); 4.41 and
4.77 (2 × d, 2H, J ) 12.0 Hz, OCH2Ph), 4.90 (m, 2H, H-4, H-9),
5.55 (d, 1H, H-5, J 5,6 ) 7.0 Hz), 5.64 (d, 1H, H-7, J 6,7 ) 12.0
Hz), 5.65 (d, 1H, H-1, J 1,2 ) 5.0 Hz), 5.97 (dd, 1H, H-6); 7.00-
7.35 (m, 15H, Harom); 13C NMR (C6D6) δ 24.6, 25.1, 26.5, 26.7,
67.0, 70.2, 70.8, 71.6, 73.3, 73.5, 74.7, 75.1, 77.7, 78.0, 97.1,
103.0, 108.2, 108.8, 123.1, 126.9-128.5, 138.9, 139.1, 153.1.
(E)-32: 1H NMR δ 1.34, 1.35, 1.45, 1.52 (4 × s, 12H, 2 ×
C(CH3)2), 3.82 (dd, 1H, H-13′, J 13,12 ) 3.0 Hz, J 13,13′ ) 11.0 Hz),
3.86 (dd, 1H, H-13, J 13,12 ) 5.5 Hz), 3.92 (dd, 1H, H-11, J 11,10
) 6.5 Hz, J 11,12 ) 9.0 Hz), 4.40 (ddd, 1H, H-12), 4.25 (dd, 1H,
2.0 Hz), 7.05-7.40 (m, 15H, Harom); 13C NMR (C6D6) δ 23.5,
24.0, 25.4, 25.5, 62.7, 63.7, 67.8, 70.5, 70.8, 71.9, 72.6, 72.8,
74.2, 75.3, 76.3, 82.2, 96.2, 107.3, 108.3, 126.2-127.7 129.5,
129.9, 137.3, 137.7, 138.2. Anal. Calcd for C40H47N3O10: C,
67.30, H, 6.64, N, 5.89. Found: C, 67.46, H, 6.84, N, 5.97.
(Z)-8,12-An h ydr o-9,10,11,13-tetr a-O-ben zyl-6,7-dideoxy-
1,2:3,4-d i-O-isop r op ylid en e-r-D-glycer o-D-gu lo-D-ga la cto-
tr id ec-6-en o-1,5-p yr a n ose (14). The phosphonium salt 8
(209 mg; 0.33 mmol) was reacted with aldehyde 5 (183 mg;
0.33 mmol) as described for the preparation of 10 to afford,
after flash chromatography (4:1 cyclohexane-ethyl acetate),
198 mg (77%) of the olefin 14 exclusively as Z-isomer, as a
H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0 Hz), 4.32 (dd, 1H, H-10, J 10,9
)
1
syrup: [R]D ) +5 (c 0.5); H NMR (C6D6) δ 1.06, 1.10, 1.50,
3.0 Hz), 4.33 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 2.0 Hz), 4.40
(d, 1H, H-5, J 5,6 ) 5.0 Hz), 4.56 and 4.63 (2 × d, 2H, J ) 12.0
Hz, OCH2Ph), 4.60 and 4.64 (2 × d, 2H, J ) 12.0 Hz, OCH2-
Ph), 4.65 (dd, 1H, H-3), 4.68 and 4.85 (2 × d, 2H, J ) 12.0 Hz,
OCH2Ph), 4.95 (d, 1H, H-9), 5.60 (d, 1H, H-1), 6.10 (d, 1H, H-7,
J 7,6 ) 15.0 Hz), 6.20 (dd, 1H, H-6), 7.20-7.40 (m, 15H, Harom);
13C NMR (CDCl3) δ 24.3, 24.9, 26.0, 26.1, 67.9, 68.5, 70.2, 70.6,
73.1, 73.4, 73.7, 74.4, 77.2, 96.5, 101.1, 108.4, 109.2, 126.6,
127.2-128.4, 151.3.
1.64 (4 × s, 12H, 2 × C(CH3)2), 3.33 (t, H, H-9, J 9,8 ≈ J 9,10
≈
10.0 Hz), 3.51 (ddd, 1H, H-12, J 12,11 ) 9.0 Hz, J 12,13 ) 1.0 Hz,
J 12,13′ ) 3.5 Hz), 3.56 (dd, 1H, H-13, J 13,13′ ) 11.0 Hz), 3.70
(dd, 1H, H-13′), 3.79 (t, 1H, H-10, J 10,11 ) 9.0 Hz), 3.92 (t, 1H,
H-11), 3.91 (dd, 1H, H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0 Hz, J 4,3 ) 8.0
Hz), 4.17 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 2.5 Hz), 4.34 and
4.47 (2 × d, 2H, J ) 12.0 Hz, OCH2Ph), 4.39 (dd, 1H, H-3, J 3,4
) 8.0 Hz), 4.40 (t, 1H, H-8, J 8,7 ) 9.0 Hz), 4.51 and 4.74 (2 ×
d, 2H, J ) 11.0 Hz, OCH2Ph), 4.72 and 4.92 (2 × d, 2H, J )
11.0 Hz, OCH2Ph), 4.91 (s, 2H, OCH2Ph), 4.98 (d, 1H, H-5,
J 5,6 ) 8.0 Hz), 5.54 (d, 1H, H-1), 5.76 (dd, 1H, H-7, J 7,6 ) 12.0
Hz), 6.21 (dd, 1H, H-6), 7.00-7.32 (m, 20H, Harom); 13C NMR
(C6D6) δ 24.4, 24.9, 26.3, 26.5, 64.5, 69.3, 70.7, 71.5, 73.5, 73.6,
75.1, 75.6, 76.7, 78.6, 79.7, 82.9, 87.4, 97.2, 108.3, 109.0, 127.2-
128.3, 130.1, 131.8, 139.1, 139.2, 139.3, 139.4. Anal. Calcd
for C47H54O10: C, 72.47, H, 6.99. Found: C, 72.17, H, 6.93.
Eluted second was a 1:2.5 mixture of (E)-12 and (Z)-12 (170
mg, 42%). Flash chromatography (30:1 toluene-acetone) gave
pure samples of these isomers. Eluted first was (Z)-12 as an
oil: [R]D ) -27 (c 0.4); 1H NMR δ 1.25, 1.30, 1.45, 1.46 (4 × s,
12H, 2 × C(CH3)2), 3.47 (ddd, 1H, H-12, J 12,11 ) 9.5 Hz, J 12,13
) 6.0 Hz, J 12,13′ ) 10.0 Hz), 3.59 (dd, 1H, H-10, J 10,9 ) 2.6 Hz,
J 10,11 ) 9.5 Hz), 3.68 (dd, 1H, H-13, J 13,13′ ) 11.0 Hz), 3.76 (dd,
1H, H-13′), 3.80 (d, 1H, H-9), 3.82 (t, 1H, H-11), 4.19 (d, 1H,
H-8, J 8,7 ) 5.8 Hz), 4.23 (dd, 1H, H-4, J 4,3 ) 8.0 Hz, J 4,5 ) 2.0
Hz), 4.28 (dd, 1H, H-2, J 2,1 ) 5.0 Hz, J 2,3 ) 2.5 Hz), 4.50 (dd,
1H, H-3), 4.53 and 4.89 (2 × d, 2H, J ) 10.5 Hz, OCH2Ph),
4.62 and 4.68 (2 × d, 2H, J ) 12.0 Hz, OCH2Ph), 4.75 (dd, 1H,
H-5, J 5,6 ) 6.8 Hz), 4.76 and 4.84 (2 × d, 2H, J ) 12.0 Hz,
OCH2Ph), 5.53 (d, 1H, H-1), 5.61 (dd, 1H, H-6, J 6,7 ) 12.0 Hz),
5.72 (dd, 1H, H-7), 7.10-7.42 (m, 20H, Harom); 13C NMR (C6D6)
δ 24.5, 25.2, 26.4, 26.5, 66.7, 70.9, 71.1, 72.0, 73.6, 74.8, 75.2,
(Z/E)-Met h yl 8,12-An h yd r o-2,3,4,9,10,11,13-h ep t a -O-
ben zyl-6,7-d id eoxy-r-D-glycer o-L-m a n n o-D-glu co-tr id ec-
6-en op yr a n osid e (15). A mixture of phosphonium salt 9 (226
mg; 0.27 mmol), activated 4-Å powdered molecular sieves (240
mg), anhydrous THF (1 mL), and HMPA (0.5 mL) was cooled
to -30 °C. To this suspension was added n-BuLi (169 µL, 0.27
mmol of 1.6 M solution in hexane), followed by the aldehyde 1
(210 mg; 0.38 mmol) in anhydrous THF (1.0 mL). The