Guerrini et al.
12.5 Hz), 4.78 (d, 1H, J ) 11.0 Hz), 4.70 (d, 1H, J ) 11.0 Hz),
4.59 (d, 1H, J ) 11.0 Hz), 4.55 (d, 1H, J ) 11.6 Hz), 4.49 (d, 1H,
J ) 11.6 Hz), 4.15 (dd, 1H, J1)8.5 Hz, J ) 10.0 Hz, H3′), 4.10
(d, 1H, J ) 10.0 Hz, NH), 3.92 (dd, 1H, J1)3.0 Hz, J2)10.0 Hz,
H1′), 3.84 (dd, 1H, J1)3.0 Hz, J2)10.0 Hz, H2′), 3.80 (t, 1H, J )
8.5 Hz, H4′), 3.70-3.62 (m, 3H, 2H of CH2 and 1H of H5′), 3.51
(dt, 1H, J1)3.2 Hz, J2)9.6 Hz, H6′), 1.44 (s, 3H, Me), 1.37 (s,
3H, Me), 1.18 (s, 9H, 3Me), 0.93 (s, 9H, 3Me). 13C NMR
(CDCl3): δ 172.9, 138.9, 138.5, 138.4, 138.2, 128.7, 128.6, 128.6,
128.5, 128.1, 128.0, 127.8, 127.7, 127.6, 127.4, 126.2, 114.5, 88.2,
80.2, 79.3, 79.1, 78.8, 77.5, 75.1, 75.0, 73.5, 72.1, 69.4, 64.6, 57.1,
39.2, 24.9, 23.0, 22.6, 20.1. Anal. Calcd for C48H61NO9S: C, 69.62;
H, 7.43; N, 1.69. Found: C, 69.43; H, 7.51; N, 1.65.
)5.0 Hz, J2)9.0 Hz, H of CH2), 3.42 (d, 1H, J2)9.0 Hz, H2′),
3.38 (dd, 1H, J1)5.0 Hz, J2 )7.5 Hz, H6′), 1.08 (s, 9H, 3Me),
0.83 (s, 9H, 3Me). 13C NMR (CDCl3): relevant resonances at δ
172.7, 138.9, 138.5, 138.3, 138.1, 136.9, 128.8-126.3, 110.5, 85.1,
82.6, 77.1, 76.6, 75.3, 75.0, 74.6, 73.8 (2 CH2), 72.2, 68.6, 62.0,
57.6, 35.4, 23.8, 23.2. Anal. Calcd for C52H61NO9S: C, 71.29; H,
7.02; N, 1.60. Found: C, 71.49; H, 7.13; N, 1.51.
(2S,5R,1′R)-17. The dioxolanone (2S,5S)-1 (0.14 g, 0.83 mmol)
was reacted with the imine (S)-9 (0.17 g, 0.26 mmol). Silica gel
column chromatography of the crude compound (n-hexane/EtOAc,
7:3) afforded (2S,5R,1′R)-17 (0.11 g, 0.13 mmol, 58%): [R]20
D
+52.1 (c 0.8, CHCl3). IR (Nujol, cm-1): 2961, 1793, 1453, 1365,
1151, 1068. MS m/z 708 (M)+, 560, 503, 432, 181. HRMS m/z
1
calcd for C40H53NO8S [M]+, 707.3492; m/z found, 707.3505. H
(2S,5R,1′S)-14. The dioxolanone (2S,5S)-2 (0.16 g, 0.73 mmol)
was reacted with imine (S)-8 (0.15 g, 0.23 mmol). Silica gel column
chromatography of the crude compound (n-hexane/EtOAc, 7:3)
afforded (2S,5R,1′S)-14 (0.17 g, 0.20 mmol, 88%): [R]20D -2.9 (c
0.40, CHCl3). IR (Nujol, cm-1): 2869, 1788, 1452, 1363, 1071.
MS (m/z): 773 (M - Me3HCO2)+, 656, 551, 181, 105. HRMS
m/z calcd for C52H61NO9S [M]+, 875.4067; m/z found, 875.4054.
1H NMR (CDCl3): δ 7.75-7.65 (m, 2H, arom), 7.40-7.20 (m,
23H, arom), 5.39 (s, 1H, O-CH-O), 4.87 (d, 2H, J ) 11.2 Hz),
4.81 (d, 2H, J ) 11.2 Hz), 4.65 (m, 2H), 4.60 (d, 1H, J ) 10.8
Hz), 4.57 (d, 1H, J ) 12.0 Hz), 4.49 (d, 1H, J ) 12.0 Hz), 4.18
(dd, 1H, J1)0.8 Hz, J2)10.4 Hz), 3.77 (dd, 1H, J1)3.2 Hz, J2)11.2
Hz), 3.60-3.57 (m, 2H), 3.55 (dd, 1H, J1)2.0 Hz, J2)11.2 Hz),
3.57-3.46 (m, 1H), 3.37 (dd, 1H, J1)0.8 Hz, J2)9.2 Hz), 3.20
(m, 1H), 1.23 (s, 9H, 3Me), 0.87 (s, 9H, 3Me). 13C NMR (CDCl3):
relevant resonances at δ 172.7, 138.8, 138.5, 138.3, 138.1, 136.8,
128.9-126.2, 110.7 (O-CH-O), 87.5, 79.2, 78.2, 77.6, 77.3, 76.9,
76.0, 75.3, 75.1, 73.9, 68.9, 61.4, 57.6, 35.4, 23.9, 23.4. Anal. Calcd
for C52H61NO9S: C, 71.29; H, 7.02; N, 1.60. Found: C, 71.06; H,
7.15; N, 1.55.
NMR (CDCl3): δ 7.40-7.20 (m, 15H, arom), 4.72 (d, 1H, J )
11.2 Hz), 4.67 (d, 1H, J ) 1.2 Hz), 4.62 (d, 1H, J ) 12.0 Hz),
4.64-4.50 (m, 3H, 2H of CH2 and 1H of H3′), 4.53 (d, 1H, J )
12.0 Hz), 4.43 (dd, 1H, J1)0.8 Hz, J2)7.6 Hz, H2′), 4.37 (d, 1H,
J ) 6.8 Hz, NH), 4.24 (m, 1H, H5′), 4.07 (t, 1H, J ) 4.5 Hz, H4′),
3.65 (dd, 1H, J1)0.8 Hz, J2)6.8 Hz, H1′), 3.56 (dd, 1H of CH2,
J1 )5.2 Hz, J2)10.0 Hz), 3.52 (dd, 1H, J1)5.6 Hz, J2)10.8 Hz,
of CH2), 1.48 (s, 3H, Me), 1.40 (s, 3H, Me), 1.30 (s, 9H, 3 Me),
0.97 (s, 9H, 3 Me). 13C NMR (CDCl3): δ 172.8, 138.1, 138.0,
137.8, 128.3-127.5, 113.7, 84.1, 83.3, 82.4, 80.0, 78.2, 73.2, 71.6,
69.8, 59.3, 56.6, 39.2, 24.9, 23.0, 22.9, 18.1. Anal. Calcd for C40H53-
NO8S: C, 67.87; H, 7.55; N, 1.98. Found: C, 67.94; H, 7.46; N,
1.90.
(2S,5R,1′R)-18. The dioxolanone (2S,5S)-2 (0.19 g, 0.88 mmol)
was reacted with the imine (S)-9 (0.18 g, 0.27 mmol). Silica gel
column chromatography of the crude compound (n-hexane/EtOAc,
7:3) afforded (2S,5R,1′R)-18 (0.170 g, 0.22 mmol, 80%): [R]20
D
+62.8 (c 0.8, CHCl3). IR (Nujol, cm-1): 2981, 1794, 1375, 1254,
1071. MS (m/z): 756 (M)+, 608, 536, 428, 372, 324, 236, 181.
HRMS m/z calcd for C44H53NO8S [M]+, 755.3492; m/z found,
755.3479. 1H NMR (CDCl3): δ 7.85-7.80 (m, 2H, arom), 7.40-
7.20 (m, 18H, arom), 5.59 (s, 1H, O-CH-O), 4.63 (d, 1H, J )
11.5 Hz), 4.60 (d, 1H, J ) 11.5 Hz), 4.58-4.54 (m, 5H, 2CH2 and
1H of H3′), 4.29 (d, 1H, J ) 7.6 Hz, NH), 4.25 (m, 1H, H5′), 4.18
(dd, 1H, J1)1.6 Hz, J2)6.4 Hz, H2′), 3.96 (t, 1H, J ) 4.0 Hz,
H4′), 3.95 (dd, 1H, J1)2.0 Hz, J2)4.8 Hz, H1′), 3.50 (dd, 1H of
CH2, J1)6.0 Hz, J2)10.4 Hz), 3.46 (dd, 1H of CH2, J1)4.8 Hz,
J2)10.4 Hz), 1.00 (s, 9H, 3Me), 0.89 (s, 9H, 3Me). 13C NMR
(CDCl3): δ 172.0, 138.6, 138.2, 138.1, 136.8, 128.6-127.8, 126.3,
110.0, 85.1, 84.8, 83.7, 82.3, 80.4, 73.6, 72.9, 71.8, 69.9, 62.0, 56.3,
35.4, 23.8, 22.9. Anal. Calcd for C44H53NO8S: C, 69.91; H, 7.07;
N, 1.85. Found: C, 69.73; H, 7.17; N, 1.75.
(2S,5R,1′R)-15. The dioxolanone (2S,5S)-1 (0.14 g, 0.83 mmol)
was reacted with imine (S)-9 (0.17 g, 0.26 mmol). Silica gel column
chromatography of the crude compound (n-hexane/EtOAc, 7:3)
afforded (2S,5R,1′R)-15 (0.169 g, 0.20 mmol, 89%): [R]20D +31.5
(c 0.5, CHCl3). IR (Nujol, cm-1): 2962, 1790, 1454, 1281, 1082.
MS m/z 828 (M)+, 680, 552, 488, 444, 354, 181. HRMS m/z calcd
1
for C48H61NO9S [M]+, 827.4067; m/z found, 827.4078. H NMR
(CDCl3): δ 7.40-7.10 (m, 20H, arom), 5.28 (d, 1H, J ) 13.0 Hz),
4.99 (d, 1H, J ) 11.5 Hz), 4.82 (d, 1H, J ) 13.0 Hz), 4.71 (d, 1H,
J ) 11.5 Hz), 4.59 (d, 1H, J ) 11.5 Hz), 4.52 (d, 1H, J ) 11.5
Hz), 4.46 (d, 1H, J ) 12.0 Hz), 4.43 (d, 1H, J ) 12.0 Hz), 4.36 (t,
1H, J ) 6.0 Hz), 4.29 (d, 1H, J ) 10.0 Hz), 4.02 (dd, 1H, J1)3.2
Hz, J2)10.0 Hz), 3.99 (d, 1H, J ) 2.0 Hz), 3.85 (dd, 1H, J1)3.2
Hz, J2)10.0 Hz), 3.67 (dd, 1H, J1)2.0 Hz, J2)8.8 Hz), 3.68-
3.50 (m, 3H, 2H of CH2 and 1 CH), 1.53 (s, 3H, Me), 1.31 (s, 3H,
Me), 1.20 (s, 9H, 3Me), 0.95 (s, 9H, 3Me). 13C NMR (CDCl3):
relevant resonances at δ 172.7, 136.6, 139.1, 138.1, 137.9, 128.7-
125.9, 114.4, 86.3, 81.3, 81.2, 77.0, 74.5, 73.6, 73.4, 72.3, 72.0,
69.3, 61.8, 57.0, 39.3, 24.9, 22.9, 22.8, 20.6. Anal. Calcd for C48H61-
NO9S: C, 69.62; H, 7.43; N, 1.69. Found: C, 69.58; H, 7.35; N,
1.60.
(2S,5R,1′S)-16. The dioxolanone (2S,5S)-2 (0.20 g, 0.91 mmol)
was reacted with imine (S)-9 (0.19 g, 0.28 mmol). Silica gel column
chromatography of the crude compound (n-hexane/EtOAc, 7:3)
afforded (2S,5R,1′S)-16 (0.17 g, 0.20 mmol, 87%): [R]20D -1.1 (c
2.0, CHCl3). IR (Nujol, cm-1): 2864, 1784, 1455, 1363,1065. MS
(m/z): 875 (M),+ 656, 551, 181, 105. HRMS m/z calcd for C52H61-
NO9S [M]+, 875.4067; m/z found, 875.4080. 1H NMR (CDCl3): δ
7.65-7.60 (m, 2H, arom), 7.40-7.10 (m, 18H, arom), 5.33 (s, 1H,
O-CH-O), 4.91 (d, 1H, J ) 11.0 Hz), 4.86 (d, 1H, J ) 11.0 Hz,
CH), 4.74 (d, 1H, J ) 12.0 Hz), 4.63 (d, 1H, J ) 12.0 Hz), 4.62
(d, 1H, J ) 11.0 Hz), 4.54 (d, 1H, J ) 10.5 Hz), 4.53 (d, 1H, J )
12.0 Hz), 4.47 (d, 1H, J ) 11.0 Hz), 4.47 (d, 1H, J ) 12.0 Hz),
4.17 (d, 1H, J ) 10.5 Hz, H1′), 3.93 (t, 1H, J ) 9.0 Hz, H3′), 3.93
(d, 1H, J ) 2.0 Hz, H5′), 3.59 (dd, 1H of CH2, J1)7.5 Hz, J2)9.0
Hz), 3.53 (dd, 1H, J1)2.0 Hz, J2)9.0 Hz, H4′), 3.44 (dd, 1H, J1
(2S,5R,1′R)-19 and (2S,5R,1′S)-20. The dioxolanone (2S,5S)-1
(0.26 g, 1.52 mmol) was reacted with imine (S)-11 (0.14 g, 0.40
mmol). Silica gel column chromatography of the crude compound
(n-hexane/EtOAc, 11:9) afforded (2S,5R,1′R)-19 (0.19 g, 0.35
mmol, 87%). [0.02 g of a 1.5:1 mixture of (2S,5R,1′S)-20/
(2S,5R,1′R)-19 was isolateted along with the major product].
(2S,5R,1′R)-19: [R]20 +16.1 (c 0.45, CHCl3). IR (Nujol, cm-1):
D
2981, 1794, 1375, 1254, 1084. MS (m/z): 534 (M + 1)+, 349,
291, 172. HRMS m/z calcd for C25H44NO9S [M+1]+, 534.2737;
1
m/z found, 534.2736. H NMR (CDCl3): δ 5.59 (d, 1H, J ) 4.8
Hz, H6′), 4.57 (dd, 1H, J1)2.4, J2)8.0 Hz, H4′), 4.48 (d, 1H, J )
3.2 Hz, NH), 4.32 (m, 1H, H2′), 4.30 (dd, 1H, J1)1.6, J2)8.0 Hz,
H3′), 4.28 (dd, 1H, J1)2.4 Hz, J2)4.8 Hz, H5′), 3.88 (dd, 1H,
J1)2.5, J2)3.2 Hz, H1′), 1.58 (s, 3H, Me), 1.57 (s, 3H, Me), 1.52
(s, 3H, Me), 1.48 (s, 3H, Me), 1.34 (s, 3H, Me), 1.33 (s, 3H, Me),
1.28 (s, 9H, 3Me), 0.97 (s, 9H, 3Me). 13C NMR (CDCl3): δ 172.6,
113.8, 110.0, 109.2, 97.1, 80.7, 74.1, 71.2, 71.0, 64.5, 57.9, 56.9,
39.3, 26.4, 26.0, 25.2, 24.8 (3 Me), 24.4, 23.5, 23.2 (3 Me), 18.0.
Anal. Calcd for C25H43NO9S: C, 56.26; H, 8.12; N, 2.62. Found:
C, 56.43; H, 8.17; N, 2.55.
1
(2S,5R,1′S)-20. H NMR (CDCl3): δ 5.51 (d, 1H, J ) 4.8 Hz,
H6′), 5.15 (d, 1H, J ) 9.2 Hz, NH), 4.66 (dd, 1H, J1)1.0 Hz,
J2)8.4 Hz, H3′), 4.56 (dd, 1H, J1)1.6, J2)8.4 Hz, H4′), 4.25 (dd,
6792 J. Org. Chem., Vol. 71, No. 18, 2006