Ch lor in a tion of 9. CPG-bound 9 (1 g) was added to acetyl
chloride (5 mL), MeOH (0.2 mL), and acetic acid (0.4 mL). The
mixture was stirred at room temperature for 2 d, washed with
DCM, acetone, MeOH, and DCM, and dried to generate C-
glycosylation donor 9.
CDCl3) (R/S ) 1:1) δ 171.4, 171.32, 171.30, 171.2, 171.14, 171.12,
75.7, 73.5, 73.4, 71.9, 71.8, 70.3, 70.0, 69.2, 68.9, 68.8, 68.0, 67.9,
63.1, 62.99, 62.97, 52.5, 49.7, 49.6, 34.7, 33.5, 32.0, 30.6, 28.6,
28.4, 28.2, 23.4, 23.3, 22.7, 22.6, 21.4, 21.13, 21.0, 20.9, 15.8;
ESI-MS 561.2 [M + H]+; HRMS calcd for C25H39NO13Na [M +
Na]+ 584.5651, found m/z 584.2328 [M + Na]+.
Meth yl 5-a ceta m id o-3,5-d id eoxy-2-C-(h yd r oxyd eca h y-
d r o-2-n a p h th a la n eyl)-D-er yth r o-L-m a n n o-n on on a te (14): 1H
NMR (500 MHz, MD3OD) (R/S ) 1:1) δ 3.82 (2s, 6H, COOCH3),
3.85-3.40 (m, 14H), 2.53 (m, 2H), 2.01 (s, 6H, NHCOCH3), 1.99
(m, 2H), 1.95-0.8 (m, 34H, decahydro-2-naphthalene); 13C NMR
(500 MHz, MD3OD) (R/S ) 1:1) δ 174.9, 166.8, 87.9, 79.7, 79.4,
76.9, 75.8, 73.0, 72.9, 70.5, 69.6, 64.7, 64.6, 54.1, 53.2, 47.5, 36.6,
36.0, 31.8, 31.6, 28.4, 28.0, 26.6, 26.1, 22.7, 21.9; ESI-MS 460.3
[M + H]+, 482.2 [M + Na]+; HRMS calcd for C22H38NO9 [M +
H]+ 460.5385, found m/z 460.2556 [M + H]+.
Meth yl 5-a ceta m id o-4,7,8,9,tetr a -O-a cetyl-2,6-a n h yd r o-
3,5-d id eoxy-2-C-(h yd r oxyd eca h yd r o-2-n a p h t h a la n yl)-D-
er yth r o-L-m a n n o-n on on a te (15): 1H NMR (500 MHz, CDCl3)
(R/S ) 1:1) δ 5.08 (m, 2H), 5.31 (dd, 2H, J ) 2, 8 Hz), 5.14 (m,
2H, NH), 4.76 (m, 2H), 4.33 (m, 2H), 4.14-3.98 (m, 6H), 3.80 (s,
6H, OCH3), 2.50 (dd, 2H, J ) 4.5, 12.5 Hz), 2.16, 2.12, 2.05, 2.04
(s, 4 × 6H, COCH3), 1.92 (t, 2H, J ) 12.5 Hz), 1,8-1.14 (m, 32
H, decahydro-2-naphthalene); 13C NMR (300 MHz, CDCl3) (R/S
) 1:1) δ 171.3, 171.0, 170.9, 170.7, 170.4, 170.2, 73.5, 73.4, 70.6,
69.0, 68.9, 68.0, 62.9, 62.7, 52.6, 52.5, 49.8, 35.1, 33.2, 32.9, 30.7,
30.5, 30.2, 29.9, 27.3, 26.9, 26.7, 26.2, 25.1, 25.0, 23.4, 21.4, 21.1,
21.0, 20.9, 20.0, 14.3, 13.3, 12.2; ESI-MS 628.3 [M + H]+, 650.2
[M + Na]+; HRMS calcd for C30H45NO13Na [M +Na]+ 650.6662,
found m/z 650.2790 [M + Na]+.
Met h yl 5-a cet a m id o-3,5-d id eoxy-2-C-[h yd r oxy-4-(ter t-
bu tylcycloh exyl)]-D-er yth r o-L-ma n n o-n on on ate (16): 1H NMR
(500 MHz, MD3OD) δ 3.81 (s, 3H, COOCH3), 3.85-3.40 (m, 7H),
2.54 (dd, 1H, J ) 4.5, 13 Hz), 2.00 (s, 3H, NHCOCH3), 2.00 (m,
1H), 1.7-1.15 (m, 9H, cyclohexane), 0.85 (s, 9H, C(CH3)3); 13C
NMR (300 MHz, MD3OD) δ 175.4, 174.7, 87.8, 75.8, 75.5, 73.1,
72.9, 70.5, 69.6, 64.6, 54.1, 53.2, 36.1, 33.4, 33.2, 32.9, 30.8, 28.0,
23.5, 23.49, 22.7; ESI-MS 462.3 [M + H]+, 484.2 [M + Na]+;
HRMS calcd for C22H39NO9Na [M + Na]+ 484.5354, found m/z
484.2521 [M + Na]+.
Meth yl 5-a ceta m id o-4,7,8,9,tetr a -O-a cetyl-2,6-a n h yd r o-
3,5-dideoxy-2-C-[h ydr oxy-4-(ter t-bu tylcycloh exyl)]-D-er yth r o-
L-m a n n o-n on on a te (17): 1H NMR (500 MHz, CDCl3) δ 5.42
(dt, 1H, J ) 2.5, 8 Hz), 5.30 (dd, 1H, J ) 2.5, 8 Hz), 5.16 (bd,
1H, J ) 10 Hz, NH), 4.76 (m, 1H), 4.32 (dd, 1H, J ) 2.4, 12.3
Hz), 4.07 (dd, 1H, J ) 6.2, 12.3 Hz), 3.99 (m, 2H), 3.79 (s, 3H,
OCH3), 2.57 (s, 1H, OH), 2.43 (dd, J ) 4.5, 12.4 Hz), 2.16, 2.12,
2.05, 2.02, (4s, 4 × 3H, COCH3), 1.97 (t, J ) 12.4, 12.4 Hz), 1.87
(s, 3H, NHCOCH3) 1.19-1.80 (m, 9H, cyclohexane), 0.88 (s, 9H,
C(CH3)3); ESI-MS 630.3 [M + H]+, 652.3 [M + Na]+.
Meth yl 5-a ceta m id o-3,5-d id eoxy-2-C-(h yd r oxy-cyclop en -
tyl)-D-er yth r o-L-m a n n o-n on on a te (18): 1H NMR (500 MHz,
MD3OD) δ 3.79 (s, 3H, COOCH3), 3.86-3.40 (m, 7H), 2.62 (dd,
1H, J ) 4.5, 13 Hz), 2.00 (s, 3H, NHCOCH3), 2.00 (m, 1H), 1.92-
1.31 (m, 8H, cyclopentane); 13C NMR (300 MHz, MD3OD) δ
175.4, 174.7, 86.5, 86.2, 75.9, 72.9, 70.4, 69.4, 64.7, 54.2, 53.2,
37.2, 36.6, 35.4, 30.8, 24.9, 22.7; ESI-MS 392.3 [M + H]+; HRMS
calcd for C17H29NO9Na [M + Na]+ 414.4025, found m/z 414.1730
[M + Na]+.
Solid -P h a se Syn th esis of C-Glycosid es. CPG-bound C-
glycosylation donor 10 (500 mg, 0.1 mmol) and electrophile (0.5
mmol) were added to a 50 mL round-bottom flask equipped with
magnetic stir bar and dried under high vacuum for 6 h. Freshly
prepared SmI2 catalyst (10 mL) was added, and the reaction
mixture was stirred overnight at room temperature. The beads
were recovered and washed four times (10 mL × 4) with THF,
saturated aq Na2S2O3, aq NaHCO3, water, acetone, MeOH, and
DCM to obtain beads with off-white color. After the beads were
dried under vacuum, they were suspended in 7 mL of dry
methanol and NaOMe (catalytic amount) was added. The
reaction mixture was stirred at room temperature overnight. The
resulting mixture was washed extensively with methanol. The
solvent washes were combined and evaporated to dryness. The
residue was passed through a small G-25 spin column to remove
salt. Acetylation of C-glycoside was undertaken to permit the
full assignment of its NMR spectrum.
Acetyla tion of C-Glycosid e. To a solution of C-glycoside (40
µmol) in pyridine (350 µL) was added acetic anhydride (150 µL,
1.5 mmol). The solution was stirred overnight at room temper-
ature and evaporated to dryness. The residual pyridine and
acetic anhydride were removed by coevaporation with toluene,
and the residue was purified by silica gel chromatography.
Meth yl 5-acetam ido-3,5-dideoxy-2-C-(h ydr oxybisben zyl)-
D-er yth r o-L-m a n n o-n on on a te (10): 1H NMR (400 MHz, MD3-
OD) δ 7.31-7.11 (m, 10H, Ar), 3.87-3.47 (m, 7H), 3.78 (1s, 3H,
COOCH3), 2.50 (dd, 1H), 2.01 (s, 3H, NHCOCH3), 1.98 (t, 1H);
13C NMR (400 MHz, MD3OD) δ 175.4, 174.7, 174.0, 139.2, 139.0,
135.8, 132.4, 132.2, 130.7, 129.6, 128.7, 128.6, 127.9, 127.1, 127.0,
88.2, 79.1, 75.6, 75.6, 73.8, 73.5, 72.9, 70.3, 69.2, 68.9, 68.6, 64.7,
64.5, 54.4, 53.5, 52.9, 52.4, 42.9, 41.6, 41.4, 37.6, 36.0, 30.7, 22.6;
[R]20 -0.162 (c 0.5, MeOH); HRMS calcd for C27H35NO9Na [M
D
+ Na]+ 540.2210, found m/z 540.2234 [M + Na]+.
Meth yl 5-a ceta m id o-4,7,8,9,tetr a -O-a cetyl-2,6-a n h yd r o-
3,5-d id eoxy-2-C-(h yd r oxyb isb en zyl)-D-er yth r o-L-m a n n o-
n on on a te (11): 1H NMR (400 MHz, CDCl3) δ 7.36-7.16 (m,
10H, Ar), 5.35-5.27 (m, 2H, NH), 5.11 (m, 1H), 4.69 (m, 1H, J
) 4.5, 7.4, 12.6 Hz), 4.26 (dd, 1H, J ) 2.1, 12.7 Hz), 4.17-4.08
(m, 3H), 3.66 (s, 3H, COOCH3), 3.19 (0.5 ABq, 1H, CH2Ph), 2.98
(s, 1H, OH), 2.95 (ABq, 2H,CH2Ph), 2.70 (0.5 ABq, 1H, CH2Ph),
2.43 (dd, 1H, J ) 4.5, 12.7 Hz), 2.24, 2.19, 2.05, 1.99, 1.87 (5s,
5 × 3H, COCH3), 1.79, (t, J ) 12.7, 12.7 Hz); 13C NMR (400
MHz, CDCl3) δ 171.1, 170.7, 170.2, 170.1, 169.9, 136.9, 136.8,
131.4, 131.3, 127.9, 127.8, 126.5, 126.3, 86.6, 77.6, 73.4, 70.4,
68.4, 67.7, 62.5, 52.4, 49.3, 40.9, 40.6, 33.3, 23.2, 21.3, 20.9, 20.9,
20.7, 14.1; [R]20 -5.5 (c 0.9, CHCl3); HRMS calcd for C35H43
N
D
O13Na [M + Na]+ 708.2632, found m/z 708.2632 [M + Na]+.
Meth yl 5-a ceta m id o-3,5-d id eoxy-2-C-(h yd r oxyp en tyl)-D-
er yth r o-L-m a n n o-n on on a te (12): 1H NMR (500 MHz, MD3-
OD) (R/S ) 1:1) δ 3.86-3.38 (m, 14H), 3.78 (2s, 6H, COOCH3),
2.50 (dd, 1H, J ) 4.5 Hz and J ) 13.5 Hz), 2.42 (dd, 1H, J ) 4.5
and J ) 13.25), 2.02 (t, 1H, J ) 11.5 Hz), 2.00 (s, 6H,
NHCOCH3), 1.75 (t, 1H, J ) 11 Hz), 1.65 (m, 2H), 1.48-1.20
(m, 12H), 0.9 (m, 6H); 13C NMR (500 MHz, MD3OD) (R/S ) 1:1)
δ 174.8, 174.4, 85.5, 84.7, 76.6, 76.1, 75.8, 75.5, 72.8, 72.5, 70.4,
70.2, 69.2, 64.7, 64.7, 54.2, 54.1, 53.1, 53.1, 49.9, 38.0, 35.7, 32.0,
31.5, 30.8, 29.6, 29.5, 23.5, 23.5, 22.7, 22.7, 14.8; ESI-MS 394.1
[M + H]+, 416.1 [M + Na]+; HRMS calcd for C17H31NO9Na [M
+ Na]+ 416.4184, found m/z 416.1888 [M + Na]+.
Meth yl 5-a ceta m id o-4,7,8,9,tetr a -O-a cetyl-2,6-a n h yd r o-
3,5-dideoxy-2-C-(h ydr oxycyclopen th yl)-D-er yth r o-L-ma n n o-
1
n on on a te (19): H NMR (500 MHz, MD3OD) δ 5.43 (dt, 1H, J
) 2.5, 8 Hz), 5.32 (dd, 1H, J ) 2.5, 8 Hz), 5.14 (bd, 1H, J ) 10
Hz, NH), 4.76 (dt, 1H, J ) 11, 11 Hz), 4.34 (dd, 1H, J ) 2.5,
12.25 Hz), 4.14-4.01 (m, 3H), 3.79 (s, 3H, COOCH3), 2.83 (bs,
1H, OH), 2.52 (dd, 1H, J ) 4.5, 12.7 Hz), 2.16, 2.13, 2.05, 2.02
(4s, 4 × 3H, COCH3), 1.90 (m, 1H), 1.87 (s, 3H, COOCH3), 1.86-
1.52 (m, 8H, cyclopentane); ESI-MS 560.3 [M + H]+.
Meth yl 5-a ceta m id o-4,7,8,9,tetr a -O-a cetyl-2,6-a n h yd r o-
3,5-d id eoxy-2-C-(h yd r oxyp en tyl)-D-er yth r o-L-m a n n o-n on -
1
on a te (13): H NMR (500 MHz, CDCl3) (R/S ) 1:1) δ 5.46 (m,
2H), 5.42 (dt, 1H, J ) 2.5, 8 Hz), 5.38 (dt, 1H, J ) 2.5, 8 Hz),
5.14 (m, 2H, NH), 4.80 (m, 2H), 4.38 (dd, 1H, J ) 4.5, 12.5 Hz),
4.34 (dd, 1H, J ) 4.5, 12.5 Hz), 4.21-4.00 (m, 6H), 3.80 (2s, 6H,
OCH3), 2.53 (dd, 1H, J ) 4.5, 14.2), 2.45 (dd, 1H, J ) 4.5, 12.5
Hz), 2.37 (dd, 1H, J ) 4.5, 12.5), 2.18, 2.16, 2.15, 2.14, 2.13, 2.09,
2.06, 2.03, 1.91, 1.87 (10s, 30H, COCH3), 1.85 (m, 1H), 1.70 (m,
2H), 1.50-1.20 (m, 12H), 0.9 (m, 6H); 13C NMR (500 MHz,
Su p p or tin g In for m a tion Ava ila ble: 1H NMR spectra for
compounds 5, 6, and 10-19; 13C NMR spectra for compounds
5, 10-16, and 18. This material is available free of charge via
the Internet at http://pubs.acs.org.
J O0491298
J . Org. Chem, Vol. 69, No. 20, 2004 6903