8
M. XIAO ET AL.
(
3
s, 3 H, NHCOCH ), 1.71 (t, J ¼ 12.0 Hz, 1 H, H-3ax), 1.17 (d, J ¼ 6.0 Hz,
3
H, CH(CH ) ), 1.05 (d, J ¼ 6.0 Hz, 3 H, CH(CH ) ); 13 C NMR (151 MHz,
3
2
3 2
CDCl ): d 170.17, 169.47, 138.84, 138.29, 138.14, 128.35, 128.30, 128.24,
3
1
7
6
28.18, 128.13, 128.04, 127.98, 127.76, 127.75, 127.52, 127.46, 127.36, 98.98,
8.54, 77.21, 76.99, 76.78, 75.21, 73.74, 73.25, 73.07, 72.67, 70.30, 69.49,
7.59, 52.26, 51.42, 37.69, 24.55, 23.72, 23.33; HRMS (ESI-TOF) Calcd for
þ
25
ꢂ
C H NO [M þ H] : 726.3642, Found: 726.3691. 5A-b: [a] ¼ -21.00
43
52
9
D
1
(
c 0.200, CHCl ); H NMR (600 MHz, CDCl ): d 7.39 – 7.24 (m, 20 H,
3 3
ArH), 4.77 – 4.68 (m, 3 H, NH, CH Ph), 4.65 – 4.59 (m, 3 H, CH Ph), 4.54
2
2
(
1
s, 2 H, CH Ph), 4.39 (d, J ¼ 11.8 Hz, 1 H, CH Ph), 4.32 (dd, J ¼ 10.2, 1.8 Hz,
2
2
H, H-6), 4.21 (td, J ¼ 10.2, 4.8 Hz, 1 H, H-4), 4.16 (dd, J ¼ 10.8, 2.4 Hz, 1 H,
Isop
H-9a), 3.99 (dq, J ¼ 12.0, 6.0 Hz, 1 H, H-1 ), 3.94 – 3.89 (m, 1 H, H-8),
.86 – 3.83 (m, 1H,H-7), 3.81 (dd, J ¼ 10.8, 6.0 Hz, 1 H, H-9b), 3.44 (dt,
J ¼ 9.6, 9.6 Hz, 1 H, H-5), 2.59 (dd, J ¼ 13.1, 4.4 Hz, 1 H, H-3eq), 1.67 – 1.59
m, 4 H, H-3ax, NHCOCH ), 1.02 (d, J ¼ 6.0 Hz, 3 H, CH(CH ) ), 0.94 (d,
3
(
3
3 2
J ¼ 6.0 Hz, 3 H, CH(CH ) ) ; 13 C NMR (151 MHz, CDCl ): d 170.16, 169.20,
3
2
3
1
1
7
2
7
38.72, 138.58, 138.47, 138.42, 129.32, 128.36, 128.32, 128.28, 127.84, 127.67,
27.65, 127.59, 127.56, 127.53, 127.41, 97.43, 80.07, 77.21, 77.00, 76.79, 75.01,
3.30, 73.07, 73.00, 72.10, 71.23, 71.21, 70.47, 65.82, 53.22, 52.31, 38.04,
þ
3.83, 23.56, 22.19; HRMS (ESI-TOF) Calcd for C H NO [M þ H] :
4
3
52
9
26.3642, Found: 726.3691.
Methyl (2-cyclohexyl 5-acetamido-4,7,8,9-tetra-O-benzyl-3,5-dideoxy-
D-glycero-D-galacto-2-nonulopyranosid)onate (5B). Compound 5B was
obtained as colorless syrup (51.2mg, 92% yield, a:b ¼ 3:1) from the reaction
of 1 (53.0 mg, 0.0729 mmol) with 4B (22.7 lL, 0.219 mmol) in 2 mL solvent
under the conditions described above and the mixture was purified by col-
2
5
ꢂ
umn chromatography to afford 5B-a and 5B-b. 5B-a: [a] ¼ ꢁ1.00 (c
D
1
0
.100, CHCl ); H NMR (600 MHz, CDCl ): d 7.41 – 7.22 (m, 20 H, ArH),
3
3
4
.77 – 4.56 (m, 6 H, CH Ph, NH), 4.55 – 4.49 (m, 2 H, CH Ph), 4.37 (d,
2
2
J ¼ 12.0 Hz, 1 H, CH Ph), 4.04 (d, J ¼ 10.8 Hz, 1 H, H-6), 3.92 – 3.79 (m,
2
Hex
4
3
1
1
1
1
7
2
7
H, H-5, H-8, H-9a, H-1 ), 3.72 – 3.64 (m, 5 H, H-7, H-9b, COOCH ),
3
.53 (td, J ¼ 10.8, 4.2 Hz, 1 H, H-4), 2.73 (dd, J ¼ 12.6, 4.2 Hz, 1 H, H-3eq),
.90 – 1.59 (m, 6 H, CyH, H-3ax, NHCOCH ), 1.48 – 1.08 (m, 8 H, CyH);
3
3 C NMR (151 MHz, CDCl3): d 170.11, 169.54, 138.90, 138.85, 138.28,
38.16, 129.01, 128.35, 128.30, 128.25, 128.20, 128.15, 128.04, 128.02,
27.98, 127.77, 127.76, 127.52, 127.48, 127.30,99.02, 78.44, 75.23, 73.95,
3.27, 73.11, 72.71, 70.30, 69.37, 52.27, 51.24, 37.40, 34.54, 33.59, 25.41,
þ
4.48, 24.44, 23.75; HRMS (ESI-TOF) Calcd for C H NO [M þ H] :
4
6
56
9
2
5
ꢂ
1
66.3955, Found: 766.3893. 5B-b: [a] ¼ ꢁ33.00 (c 0.100, CHCl ); H
D
3
NMR (600 MHz, CDCl ): d 7.39 – 7.22 (m, 22H,ArH), 4.77 – 4.72 (m, 3 H,
3
CH Ph), 4.66 (d, J ¼ 12.1 Hz, 1 H, CH Ph), 4.61 – 4.58 (m, 2 H, CH Ph,
2
2
2
NH), 4.55 (s, 2 H, CH Ph), 4.41 – 4.37 (m, 2 H, CH Ph, H-6), 4.27
2
2