1498 J . Org. Chem., Vol. 65, No. 5, 2000
Burke and Zhao
MHz) δ 7.16-7.35 (m, 10 H), 5.96 (br d, 1 H, J ) 10.5 Hz),
5.83 (ddd, 1 H, J ) 10.5, 6, 2 Hz), 5.67 (ddd, 1 H, J ) 10.5, 6,
3 Hz), 5.37 (br d, 1 H, J ) 10.5 Hz), 4.69 (qd, 1 H, J ) 6, 4.5
Hz), 4.62 (d, 1 H, J ) 12 Hz), 4.36 (ABq, 2 H, J AB ) 11 Hz,
∆υAB ) 21.3 Hz), 4.33 (s, 2 H), 4.25 (d, 1 H, J ) 3 Hz), 4.26 (d,
1 H, J ) 3 Hz), 4.21 (d, 1 H, J ) 3 Hz), 3.58 (A of ABX, 1 H,
J AB ) 9 Hz, J AX ) 9 Hz), 3.47 (A of ABX, 1 H, J AB ) 9 Hz, J AX
) 9 Hz), 3.41 (B of ABX, 1 H, J AB ) 9 Hz, J BX ) 4.5 Hz), 3.37
(B of ABX, 1 H, J AB ) 9 Hz, J BX ) 4.5 Hz), 2.75 (m, 2 H), 1.27
(d, 3 H, J ) 6 Hz), 1.25 (d, 3 H, J ) 6 Hz), 0.89 (s, 9 H), 0.09
(s, 3 H), 0.08 (s, 3 H); 13C NMR (CDCl3, 75 MHz) δ 169.6, 168.2,
137.9, 137.5, 128.9, 128.1, 128.1, 127.7, 127.4, 125.5, 125.2,
94.4, 80.1, 76.9, 74.1, 73.5, 73.2, 73.0, 72.5, 71.9, 70.4, 69.2,
68.6, 38.01, 25.6, 20.8, 17.9, 14.4, -4.5, -4.8, MS (FAB) m/e
835.2 (M+ + Na, C40H55O9Cl3SiNa requires 835.2).
(10 mL) at 0 °C was added 52% aqueous HF solution (1.5 mL).
The reaction was quenched after 30 min with 20 mL of CH2-
Cl2, 20 mL of H2O, and 10 mL of saturated NaHCO3 aqueous
solution. The aqueous layer was extracted with CH2Cl2 (2 ×
30 mL). The combined organic phases were dried (MgSO4) and
concentrated. Flash chromatography (33% hexanes in Et2O)
afforded 690 mg (95%) desired product as a colorless oil. Data
for 31: Rf 0.26 (50% hexanes in ether); [R]23 -25.6 (c 0.626,
D
1
CHCl3); IR (thin film) 3358, 1726 cm-1; H NMR (CDCl3, 300
MHz) δ 7.18-7.25 (m, 4 H), 6.8-6.88 (m, 4 H), 5.94 (ddd, 1 H,
J ) 10.5, 6, 3 Hz), 5.81 (br d, 1 H, J ) 10.5 Hz), 5.7 (ddd, 1 H,
J ) 10.5, 6, 3 Hz), 5.35 (br d, 1 H, J ) 10.5 Hz), 4.72 (qd, 1 H,
J ) 6.7, 4.5 Hz), 4.63 (d, 1 H, J ) 12 Hz), 4.33 (d, 1 H, J ) 3
Hz), 4.29 (ABq, 2 H, J ) 11 Hz, ∆υAB ) 34.3 Hz), 4.26 (ABq,
2 H, J ) 10.5 Hz, ∆υAB ) 19 Hz), 4.14 (d, 1 H, J ) 3 Hz),
4.18-4.23 (br, 1 H), 3.96-4.07 (m, 2 H), 3.75-3.82 (m, 7 H),
2.67-2.88 (m, 3 H), 1.24 (d, 3 H, J ) 7.5 Hz), 1.22 (d, 3 H, J
) 7.5 Hz); 13C NMR (CDCl3, 75 MHz) δ 169.5, 168.2, 159.2,
159.1, 129.8, 129.7, 127.9, 127.1, 126.8, 125.6, 113.5, 94.4, 79.4,
76.7, 73.9, 73.3, 72.8, 72.4, 72.0, 68.5, 68.5, 68.3, 55.0, 38.2,
38.1, 17.5, 14.1; HRMS (FAB) m/e 779.1794 (M+ + Na,
Data for 33: Rf 0.21 (50% ether in hexanes); [R]23 24.6 (c
D
0.766, CHCl3); IR (thin film) 1716 cm-1; 1H NMR (CDCl3, 300
MHz) δ 7.2-7.4 (m, 20 H), 5.96-6.08 (m, 2 H), 5.82-5.93 (m,
2 H), 5.58 (br d, 2 H, J ) 10.0 Hz), 4.94 (s, 1 H), 4.86-4.96
(m, 2 H), 4.69 (ABq, 2 H, J ) 6.8 Hz, ∆υAB ) 16.7 Hz), 4.63 (d,
1 H, J ) 4.5 Hz), 4.58 (d, 1 H, J ) 4.5 Hz), 4.49 (d, 1 H, J )
4.3 Hz), 4.45 (ABq, 2 H, J ) 11.9 Hz, ∆υAB ) 17.6 Hz), 4.21-
4.28 (m, 1 H), 4.0-4.1 (m, 1 H), 3.88-3.96 (m, 2 H), 3.63-
3.76 (m, 3 H), 1.36 (d, 3 H, J ) 6.8 Hz), 1.21 (d, 3 H, J ) 7.1
Hz), 0.98 (d, 3 H, J ) 7.2 Hz); 13C NMR (CDCl3, 75 MHz) d
168.9, 168.6, 167.5, 138.4, 137.9, 137.8, 129.7, 129.4, 129.3,
129.2, 129.1, 129.0, 128.9, 128.4, 128.3, 128.2, 128.0, 127.9,
127.8, 127.5, 127.5, 127.1, 125.7, 125.5, 125.1, 94.3, 93.6, 78.5,
77.2, 77.1, 76.7, 76.6, 76.5, 76.3, 74.3, 74.1, 72.2, 72.1, 69.5,
C
36H43O11Cl3Na requires 779.1769).
Bis(d ih yd r op yr a n ) Hyd r oxy 2,2,2-Tr ich lor oeth yl Ester
32 a n d Tr is(d ih yd r op yr a n ) Hyd r oxy 2,2,2-Tr ich lor oeth yl
Ester s 37 a n d 38. Refer to preparation of 31. Data for 32: Rf
0.2 (50% ethyl acetate in hexanes); [R]23 -23.8 (c 0.508,
D
1
CHCl3); IR (thin film) 3440, 1726 cm-1; H NMR (CDCl3, 300
MHz) δ 7.18-7.38 (m, 10 H), 5.94 (ddd, 1 H, J ) 10.5, 6, 3
Hz), 5.81 (br d, 1 H, J ) 10.5 Hz), 5.72 (ddd, 1 H, J ) 10.5, 6,
3 Hz), 5.35 (br d, 1 H, J ) 10.5 Hz), 4.73 (qd, 1 H, J ) 6.2, 4.5
Hz), 4.63 (d, 1 H, J ) 12 Hz), 4.36 (ABq, 2 H, J AB ) 12 Hz,
∆υAB ) 32.3 Hz), 4.34 (ABq, 2 H, J AB ) 12 Hz, ∆υAB ) 9 Hz),
4.32 (d, 1 H, J ) 3 Hz), 4.21 (m, 1 H), 4.16 (d, 1 H, J ) 3 Hz),
4.06 (m, 1 H), 4.02 (qd, 1 H, J ) 6.2, 4.5 Hz), 3.89 (d, 1 H, J
) 12 Hz), 3.54 (A of ABX, 1 H, J AB ) 9 Hz, J AX ) 9 Hz), 3.47
(A of ABX, 1 H, J AB ) 9 Hz, J AX ) 9 Hz), 3.46 (B of ABX, 1 H,
J AB ) 9 Hz, J BX ) 4.5 Hz), 3.38 (B of ABX, 1 H, J AB ) 9 Hz,
J BX ) 4.5 Hz), 2.7-2.87 (m, 3 H), 1.24 (d, 3 H, J ) 6.2 Hz),
1.21 (d, 3 H, J ) 6.2 Hz); 13C NMR (CDCl3, 75 MHz) δ 169.5,
168.2, 137.7, 137.5, 128.3, 128.2, 128.1, 127.9, 127.6, 127.5,
127.2, 126.9, 125.7, 94.4, 79.5, 76.7, 74.0, 73.4, 73.1, 72.4, 72.1,
68.9, 68.5, 38.0, 17.5, 17.9, 14.1; HRMS (FAB) m/e 719.1539
(M+ + Na, C34H39O9Cl3Na requires 719.1557).
43.3, 43.1, 43.0, 16.5, 15.0, 14.89; MS (FAB) m/e 961.3 (M+
+
H, C52H54O11Cl3 requires 961.3).
Data for 34: Rf 0.31 (60% ether in hexanes); [R]23 23.8 (c
D
0.576, CHCl3); IR (thin film) 1715 cm-1; 1H NMR (CDCl3, 300
MHz) δ 7.18-7.25 (m, 6 H), 6.8-6.88 (m, 6 H), 5.96 (br d, 1 H,
J ) 10.5 Hz), 5.83 (ddd, 1 H, J ) 10.5, 6, 3 Hz), 5.68 (ddd, 1
H, J ) 10.5, 6, 3 Hz), 5.67 (ddd, 1 H, J ) 10.5, 6, 3 Hz), 5.29-
5.37 (m, 2 H), 4.62 (d, 1 H, J ) 12 Hz), 4.62-4.72 (m, 2 H),
4.29 (ABq, 2 H, J ) 11 Hz, ∆υAB ) 19 Hz), 4.17-4.32 (m, 4
H), 3.99 (m, 2 H), 3.86-3.94 (m, 1 H), 3.8 (d, 1 H, J ) 12 Hz),
3.74-3.8 (m, 10 H), 3.54 (A of ABX, 1 H, J AB ) 10.5 Hz, J AX
)
10.5 Hz), 3.45 (A of ABX, 1 H, J AB ) 10 Hz, J AX ) 10 Hz), 3.44
(A of ABX, 1 H, J AB ) 10 Hz, J AX ) 10 Hz), 3.38 (B of ABX, 1
H, J AB ) 10.5 Hz, J BX ) 4 Hz), 3.37 (B of ABX, 1 H, J AB ) 10.5
Hz, J BX ) 4 Hz), 3.31 (B of ABX, 1 H, J AB ) 10.5 Hz, J BX ) 4
Hz), 2.6-2.85 (m, 3 H), 1.27 (d, 3 H, J ) 6.5 Hz), 1.25 (d, 3 H,
J ) 6.5 Hz), 1.24 (d, 3 H, J ) 6.5 Hz), 0.89 (s, 9 H), 0.09 (s, 3
H), 0.08 (s, 3 H); 13C NMR (CDCl3, 75 MHz) δ 169.6, 169.1,
168.2, 159.1, 158.9, 130.2, 130.1, 129.7, 129.7, 129.6, 128.7,
128.1 127.9, 126.1, 125.4, 113.4, 94.5, 80.1, 77.1, 76.8, 73.9,
73.5, 73.0, 72.7, 72.6, 72.4, 72.0, 71.7, 70.4, 68.9, 68.7, 68.4,
55.0, 38.1, 38.0, 37.8, 25.7, 20.8, 17.9, 14.5, 14.3, -4.6, -4.8;
MS (FAB) m/e 1199.1 (M+ + H +Na, C59H78O16Cl3SiNa
requires 1198.4).
Data for 37: Rf 0.25 (50% ethyl acetate in hexanes); [R]23
D
33.8 (c 0.816, CHCl3); IR (thin film) 3456, 1716 cm-1; 1H NMR
(CDCl3, 300 MHz) δ 7.18-7.25 (m, 6 H), 6.8-6.88 (m, 6 H),
5.93 (ddd, 1 H, J ) 10.5, 6, 2 Hz), 5.82 (br d, 1 H, J ) 10.5
Hz), 5.72 (ddd, 1 H, J ) 10.5, 6, 2 Hz), 5.67 (ddd, 1 H, J )
10.5, 6, 2 Hz), 5.34 (br d, 1 H, J ) 10.5 Hz), 5.32 (br d, 1 H, J
) 10.5 Hz), 4.71 (qd, 1 H, J ) 6.8, 4.5 Hz), 4.66 (qd, 1 H, J )
6.8, 4.5 Hz), 4.61 (d, 1 H, J ) 12 Hz), 4.33 (ABq, 2 H, J ) 12
Hz, ∆υAB ) 13.4 Hz), 4.32 (d, 1 H, J ) 3 Hz), 4.26 (ABq, 2 H,
J ) 10.5 Hz, ∆υAB ) 20 Hz), 4.17 (m, 1 H), 4.16 (d, 1 H, J )
3 Hz), 4.07 (d, 1 H, J ) 3 Hz), 3.99 (br, 2 H), 3.8 (d, 1 H, J )
Data for 35: Rf 0.36 (75% ether in hexanes); [R]23 35.7 (c
D
0.548, CHCl3); IR (thin film) 1718 cm-1; 1H NMR (CDCl3, 300
MHz) δ 7.18-7.35 (m, 15 H), 5.96 (br d, 1 H, J ) 10.5 Hz),
5.84 (ddd, 1 H, J ) 10.5, 6, 3 Hz), 5.63-5.73 (m, 2 H), 5.34 (br
d, 2 H, J ) 10.5 Hz), 5.62 (d, 2 H), 5.6-5.74 (m, 2 H), 4.36
(ABq, 2 H, J AB ) 12 Hz, ∆υAB ) 26.4 Hz), 4.34 (s, 2 H), 4.32
(ABq, 2 H, J AB ) 12 Hz, ∆υAB ) 24.2 Hz), 4.19 (d, 1 H, J ) 3
Hz), 4.13 (d, 1 H,J ) 3 Hz), 4.04 (m, 2 H), 3.89 (d, 1 H, J ) 12
Hz), 3.88 (m, 1 H), 3.77 (quint, 1 H, J ) 6 Hz), 3.58 (A of ABX,
1 H, J AB ) 9 Hz, J AX ) 9 Hz), 3.47 (A of ABX, 2 H, J AB ) 9 Hz,
J AX ) 9 Hz), 3.41 (B of ABX, 1 H, J AB ) 9 Hz, J BX ) 4.5 Hz),
3.38 (B of ABX, 1 H, J AB ) 9 Hz, J BX ) 4.5 Hz), 3.32 (B of
ABX, 1 H, J AB ) 9 Hz, J BX ) 4.5 Hz), 2.66-2.85 (m, 3 H), 1.27
(d, 3 H, J ) 6 Hz), 1.25 (d, 6 H, J ) 6 Hz), 0.89 (s, 9 H), 0.09
(s, 3 H), 0.08 (s, 3 H); 13C NMR (CDCl3, 75 MHz) δ 169.5, 169.1,
168.2, 137.9, 137.8, 137.4, 128.81, 128.8, 128.1, 127.9, 127.7,
127.5, 127.4, 126.2, 125.6, 125.4, 94.4, 80.1, 77.1, 76.9, 74.0,
73.5, 73.3, 73.2, 73.1, 72.4, 72.1, 71.9, 70.4, 69.2, 68.9, 68.6,
38.1, 37.8, 25.6, 20.8, 17.9, 14.6, 14.4, -4.6, -4.7; HRMS (FAB)
m/e 1107.3681 (M+ + Na, C56H71O13Cl3SiNa requires 1107.3627).
Bis(d ih yd r op yr a n ) Hyd r oxy 2,2,2-Tr ich lor oeth yl Ester
31. To a solution of dimer 28 (830 mg, 0.951 mmol) in CH3CN
12 Hz), 3.77 (s, 9 H), 3.51 (A of ABX, 1 H, J AB ) 10 Hz, J AX )
9 Hz), 3.4-3.5 (m, A of ABX, 2 H; B of ABX, 1 H), 3.37 (B of
ABX, 1 H, J AB ) 10 Hz, J BX ) 4.5 Hz), 3.32 (B of ABX, 1 H,
J AB ) 10 Hz, J BX ) 4.5 Hz), 2.96 (d, 1 H, J ) 5.8 Hz), 2.64-
2.84 (m, 3 H), 1.24 (d, 3 H, J ) 6.5 Hz), 1.23 (d, 3 H, J ) 6.5
Hz), 1.22 (d, 3 H, J ) 6.5 Hz); 13C NMR (CDCl3, 75 MHz) δ
169.6, 169.1, 168.2, 159.1, 158.9, 129.9, 129.8, 129.8, 129.7,
129.6, 128.1, 127.7, 127.1, 126.3, 125.5, 113.5, 94.5, 79.4, 76.8,
73.9, 73.3, 73.1, 72.7, 72.5, 72.2, 71.8, 68.7, 68.6, 68.5, 68.4,
55.0, 38.1, 38.0 37.8, 17.6, 14.3, 14.0; HRMS (FAB) m/e
1083.3106 (M+ + Na, C53H63O16Cl3Na requires 1083.3079).
Data for 38: Rf 0.28 (50% ethyl acetate in hexanes); [R]23
D
25.8 (c 0.536, CHCl3); IR (thin film) 3420, 1715 cm-1; 1H NMR
(CDCl3, 300 MHz) δ 7.1-7.4 (m, 15 H), 5.85-6.08 (m, 4 H),
5.56 (br t, 2 H, J ) 10 Hz), 4.86-5.01 (m, 2 H), 4.66 (d, 1 H,
J ) 4.3 Hz), 4.56 (d, 1 H, J ) 4.5 Hz), 4.53 (d, 1 H, J ) 4.5
Hz), 4.49 (ABq, 2 H, J AB ) 1.9 Hz, ∆υAB ) 17.6 Hz), 4.26-4.30
(m, 1 H), 4.08-4.13 (m, 2 H), 3.83-3.90 (m, 1 H), 3.63-3.80
(m, 3 H), 1.33 (d, 3 H, J ) 7.2 Hz), 1.24 (d, 3 H, J ) 7.1 Hz),
1.11 (d, 3 H, J ) 6.8 Hz); 13C NMR (CDCl3, 75 MHz) δ 168.8,
168.7, 167.2, 138.2, 138.0, 137.6, 129.6, 129.3, 128.9, 128.8,