C.M. Nkambule et al. / Tetrahedron 67 (2011) 618e623
623
(1H, br s), 1.11 (3H, s), 0.94 (3H, s), 0.94 (3H, s); 13C NMR (75 MHz,
CDCl3): 178.2, 166.7, 138.2, 137.4, 128.4, 128.2, 128.0, 127.9, 127.8,
127.6, 127.5, 127.3, 91.2, 82.9, 81.4, 80.9, 78.1, 75.7, 75.66, 75.3, 72.2,
70.5, 69.0, 54.8, 54.2, 30.6, 28.8, 16.40, 16.36, 9.6. Anal. Calcd for
C44H48O9: C, 73.31; H, 6.71. Found: C, 73.37; H, 6.70.
(TLC, toluene/EtOAc 2:1). The reaction mixture was then cooled to
ꢀ40 ꢁC and water (0.90 mL, 49.7 mmol) was added. After stirring
for 4 h at ꢀ40 ꢁC the reaction mixture was neutralized with pyri-
dine and concentrated. The residue was dissolved in EtOAc (20 mL),
washed with water (2ꢄ20 mL), dried over MgSO4 and concen-
trated. Flash chromatography (toluene/EtOAc 10:1 to 5:1) gave 13
d
3.2.4. 2-(S)-Camphanoyl-3,4,5,6-tetra-O-benzyl-
L
-myo-inositol
(0.91 g, 94%); IR (CDCl3) 3463, 1745 cmꢀ1
;
1H NMR (300 MHz,
24
(
L
-9b). Rf 0.22 in EtOAc/PE (1:4), [
a
]
ꢀ12.8 (c 1.25, CHCl3); IR
CDCl3):
d
7.30e7.45 (20H, m), 5.74 (1H, t, J¼2.7 Hz), 4.7e5.1 (7H, m,
D
(neat) 3316, 1787, 1755 cmꢀ1 1H NMR (300 MHz, CDCl3):
;
CH2Ph), 4.54 (1H, d, J¼11.3 Hz, CH2Ph), 3.93 (1H, t, J¼9.5 Hz), 3.82
(1H, t, J¼9.6 Hz), 3.62 (1H, dd, J¼2.7, 9.6 Hz), 3.57 (1H, t, J¼9.6 Hz),
3.56 (1H, dd, J¼2.7, 9.5 Hz), 2.20 (3H, s); 13C NMR (75 MHz, CDCl3):
d
7.37e7.24 (20H, m) 5.82 (1H, t, J¼2.8 Hz), 5.01e4.51 (8H, m), 3.83
(1H, t, J¼9.4 Hz), 3.72e3.48 (4H, m), 2.36e2.26 (1H, m), 2.06e1.95
(1H, m), 1.94e1.84 (1H, m), 1.74e1.62 (1H, m), 1.57 (1H, br s), 1.11
d
170.7 (C]O), 138.8, 138.5, 138.5, 137.8, 127.8e128.8 (Ph), 83.4,
(3H, s), 1.04 (3H, s), 0.84 (3H, s); 13C NMR (75 MHz, CDCl3):
d
178.1,
82.1, 81.6, 78.6, 76.1, 76.1, 75.8, 72.3, 70.3, 69.6 (CH2Ph, inositol), 21.2
(CH3eCOOe). [MþNa]þ calcd for C36H38O7Na 602.2515, found
605.2501.
166.6, 138.3, 138.2, 138.1, 137.3, 128.5, 128.3, 128.2, 128.1, 128.0,
127.9, 127.8, 127.6, 127.5, 91.2, 82.9, 81.7, 80.3, 77.9, 75.8, 75.7, 72.2,
70.4, 69.5, 54.7, 54.1, 30.5, 28.8, 16.6, 16.3, 9.6. Anal. Calcd for
C44H48O9: C, 73.31; H, 6.71. Found: C, 73.19; H, 6.74.
Supplementary data
3.3. General method for NaH induced migration of tosyl and
tert-butyldimethylsilyl groups
Supplementary data associated with this article can be found in
To a cooled solution (0 ꢁC) of compound 10a or 11a in DMF
(0.2 M) was added NaH (1 equiv 60% dispersion in mineral oil). TLC
analysis showed no starting material remained after 30 min and the
reaction was quenched first with MeOH followed by H2O. The
mixture was taken up in EtOAc and washed successively with 2 M
HCl, then brine, and the organic layer was dried over MgSO4. The
crude mixtures were analyzed by HPLC before the pure isomers 10b
and 11b were isolated by column chromatography purification.
References and notes
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ꢀ
3.3.1. (ꢃ)-2-p-Toluenesulfonyl-3,4,5,6-tetra-O-benzyl-myo-inositol
(10b). Rf 0.3 in EtOAc/PE (1:1); mp 106e109 ꢁC; IR (CH2Cl2)
3523 cmꢀ1; 1H NMR (300 MHz, CDCl3):
d
7.98e7.95 (2H, d, J¼9 Hz),
7.61e7.45 (22H, m), 5.62 (1H, s), 5.27e4.69 (9H, m), 4.28e4.14 (2H,
m), 3.72e3.64 (2H, m), 2.96 (1H, s), 2.57 (3H, s); 13C NMR (75 MHz,
€
5523e5542; (b) Lindberg, J.; Ohberg, L.; Garegg, P. J.; Konradsson, P. Tetrahedron
2002, 58, 1387e1398.
CDCl3):
d 144.78, 138.39, 139.12, 137.99, 137.35, 129.70, 128.67,
128.52, 128.49, 128.34, 128.30, 128.07, 127.99, 127.87, 127.81, 127.79,
127.67, 127.62, 127.56, 127.53, 127.38, 127.34, 126.93, 82.62, 81.23,
80.65, 79.21, 78.42, 76.01, 75.93, 75.39, 72.76, 68.59, 65.24, 21.62.
[MþNa]þ calcd for C41H42O8S 717.2498, found 717.2471.
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M. S.; Dixit, S. S. Tetrahedron 2005, 61, 529e536; (c) Sureshan, K. M.; Sha-
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3.3.2. (ꢃ)-2-tert-Butyldimethylsilyloxy-3,4,5,6-tetra-O-benzyl-myo-
inositol (11b). Rf 0.56 in EtOAc/PE (1:2); IR (neat) 3449 cmꢀ1 1H
;
NMR (300 MHz CDCl3):
d 7.39e7.19 (20H, m), 4.95e4.69 (8H, m),
4.02 (1H, t, J¼9.6 Hz), 3.93 (1H, dd, J¼2.4, 2.8 Hz), 3.79 (1H, dd,
J¼9.2, 9.6 Hz), 3.52 (1H, dd, J¼2.4, 9.2 Hz), 3.42 (1H, dd, J¼9.2,
9.6 Hz), 3.39 (1H, dd, J¼2.8, 9.6 Hz), 2.5 (1H, br s), 0.9 (9H, s), 0.06
(6H, s); 13C NMR (75 MHz, CDCl3):
d 138.7, 138.5, 138, 128.4, 128.3,
128.2, 128.1, 127.93, 127.8, 127.7, 127.5, 127.4, 127.3, 127.2, 83.1, 81.6,
81.1, 79.3, 75.8, 75.8, 75.6, 73.4, 72.8, 70.9, 29.6, 25.8, ꢀ4.6, ꢀ4.9.
[MþH]þ calcd for C40H50O6Si 655.3455, found: 655.3455.
3.3.3. 2-O-Acetyl-3,4,5,6-tetra-O-benzyl-D-myo-inositol (13). To a so-
lution of 3,4,5,6-tetra-O-benzyl- -myo-inositol (0.90 g, 1.66 mmol)
D
in acetonitrile (50 mL) were added p-toluenesulfonic acid mono-
hydrate (30 mg, 0.16 mmol) and trimethyl orthoacetate (0.90 mL,
0.85 g, 7.07 mmol). After stirring for 2 h at room temperature the
starting material had been converted to the cyclic orthoester 12