August 1998
SYNLETT
833
"Carbohydrate Mimics, Concepts and Methods" Yves Chapleur,
Ed., Wiley VCH, 1998 pp 19-48 and references therein.
2.02-1.82 (m, 3H, H-2, CH2 bridge), 1.55, 1.38 (2s, 6H, CH3),
1.28 (d, 3H, H-6').
1
(3) a) Wang, Y.; Goekjian, P. G.; Ryckmann, D. M.; Miller, W. H.;
Babirad, S. A.; Kishi, Y. J. Org. Chem. 1992, 57, 482. b)Wei, A.;
Boy, K. M.; Kishi, Y. J. Am. Chem. Soc. 1995, 117, 9432.
c) Espinosa, J. -F.; Martín-Pastor, M.; Asensio, J. L.; Dietrich, H.;
Martín-Lomas, M.; Schmidt, R. R.; Jiménez-Barbero, J.
Tetrahedron Lett. 1995, 36, 6329. d) Espinosa, J.-F.; Cañada, F. J.;
Asensio, J. L.; Martín-Pastor, M.; Dietrich, H.; Martín-Lomas, M.;
Schmidt, R. R.; Jiménez-Barbero, J. J. Am. Chem. Soc. 1996, 118,
10862. e) Espinosa, J.-F.; Cañada, F. J.; Asencio, J. L.; Dietrich,
H.; Martin-Lomas, M.; Schmidt, R. R.; Jiminez-Barbero, J.
Angew. Chem. Int. Ed. Engl. 1996, 35, 303. f) Berthault, P.;
Birlirakis, N.; Rubinstenn, G.; Sinaÿ, P.; Desvaux, H. J. Biomol.
NMR 1996, 8, 23-35. g) Rubinstenn, G.; Sinaÿ, P.; Berthault, P. J.
Phys Chem. A 1997, 101, 2536. h) Espinosa, J.-F.; Montero, E.;
Vian, A.; Garcia, J. L.; Dietrich, H.; Schmidt, R. R.; Martin-
Lomas, M.; Imberty, A.; Cañada, F. J.; Jiminez-Barbero, J. J. Am.
Chem. Soc. 1998, 120, 1309.
(13) Selected data for 7 : H NMR (400 MHz, CDCl3): δ : 5.11 (dd,
1H, J2’,3’ 10.5 Hz, J3’,4’ 3 Hz, H-3'), 4.98 (t, 1H, J4,3 = J4,5 10 Hz, H-
4), 4.84 (d, 1H, J1,2 3.5 Hz, H-1), 4.22 (dddd, 1H, J1’,CHa 1.77 Hz,
J1’,2’ 5.87 Hz, J1’,CHb 11.83 Hz, H-1'), 2.08 (m, 1H, H-2), 1.89
(dddd, 1H, JCHb,CHa 15.4 Hz, JCHb,2 7.1 Hz, CH ), 1.46 (dddd, 1H,
JCHa,2 4.23 Hz, CH ), 1.16 (d, 3H, J6’,5’ 6.5 Hz, H-6').
b
a
(14) Carey, F.A.; Frank, W.C. J. Org. Chem. 1982, 47, 3548.
(15) Compound 9 was prepared by selective reductive opening
(NaBH3CN, M.S. 4 Å, THF, HCl, diethyl ether, 95%) of the
known 4,6-O-benzylidene acetal : Yoshimura, J.; Kawauchi, N.;
Yasumori, T.; Sato, K-I.; Hashimoto, H. Carbohydr. Res. 1984,
133, 255.
(16) Compound 10 was prepared from known17 methyl 4,6-O-
benzylidene β-D-galactopyranoside (Scheme 5).
(4) a) Phillips, M. L.; Nudelman, E.; Gaeta, F. C. A.; Perez, M.;
Singahl, A. K.; Hakomori, S. I.; Paulson, J. C. Science 1990, 250,
1130. b) Walz, G.; Aruffo, A.; Kolanus, W.; Bevilacqua, M.; Seed,
B. Science 1990, 250, 1132.
(5) a) Uchiyama, T.; Vassilec, V.P.; Kajimoto, T.; Huang, H.; Lin, C.-
C.; Wong, C.-H. J. Am. Chem. Soc. 1995, 117, 5395. b) Lin, C.-C.;
Shimazaki, M.; Heck, M.-P.; Aoki, S; Wang, R.; Kimura, T.;
Ritzen, H.; Takayama, S.; Wu, S.-H.; Weitz-Schmidt, G.; Wong,
C.-H. J. Am. Chem. Soc. 1996, 1180, 6826. c) Jahnke, W.; Kolb,
H. C.; Blommers, M. J. J; Magnani, J. L.; Ernst, B. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 2603.
(17) a) Chittenden, G. J. F. Recl. Trav. Chim. Pays-Bas 1988, 107, 607.
b) Kihlberg, J.; Frejd, T.; Jansson, K.; Magnusson, G.Carbohydr.
Res. 1986, 152, 113.
(18) Selected data for 11: [α]D20 + 35 (c 1.58, CHCl3).
(6) a) Stork, G.; Kim G.; J. Am. Chem. Soc. 1992, 114, 1087. b) Xin,
Y.-C.; Mallet, J.-M.; Sinaÿ, P. J. Chem. Soc., Chem. Commun.
1993, 864. c) Chénedé, A.; Perrin, E.; Rekaï, E. D.; Sinaÿ, P.
Synlett 1994, 420. d) Mallet, A.; Mallet, J.-M.; Sinaÿ, P.
Tetrahedron: Asymmetry 1994, 2593. e) Rubinstenn, G.; Mallet,
J.-M.; Sinaÿ, P. Tetrahedron Lett. 1998, in press. f) For a review on
silaketal tether, see Bols, M.; Skrydstrup, T. Chem. Rev. 1995, 95,
1253.
(19) Selected data for 12 : mp: 191°C (Ethyl Acetate); [α]D20 + 31 (c
1.1, CHCl3).
(20) Selected data for 13 : mp: 108 °C (Cyclohexane/Ethyl Acetate).
[α]D20 - 36 (c 1, CHCl3).
(21) Selected data for the talo compound : mp: 112°C (Cyclohexane/
1
Ethyl Acetate). [α]D20 - 41 (c 2, CHCl3). H NMR (400 MHz;
CDCl3): δ : 4.43 (d, 1H, J1,2 2Hz, H-1), 4.27 (dd, 1H, J3’,4’ 7.5 Hz,
J3’,2’ 4.5 Hz, H-3'), 4.17-4.09 (m, 2H, H-6b, H-4), 4.04 (dddd, 1H,
(7) For other approaches to this problem , see a) Giese, B.; Witzel, T.;
Angew. Chem. Int. ed. Engl. 1986, 25, 450. b) Giese, B.; Hoch,
M.; Lamberth, C. ; Schmidt, R.R. Tetrahedron Lett. 1988 , 29,
1375. c) Wei, A.; Boy, K. M.; Kishi. Y. J. Am. Chem. Soc. 1997,
117, 9432. d) Sutherlin, D. P.; Armstrong, R. W. J. Org. Chem.
1997, 62, 5267.
1
J5’,4’ 2 Hz, J5’,6’ 6.5 Hz, H-5'). H NMR (400 MHz; C2D6CO +
CDCl3)+ CCl3-CO-NCO): δ: 5.28 (dd, 1H, J3,2 5 Hz, J3,4 3.5 Hz,
H-3), 5.06 (dd, 1H, J2’,1’ 3 Hz, J2’,3’ 4.5 Hz, H-2'), 4.81 (d, 1H, J1,2
2.5 Hz, H-1).
(22) Selected data for 17 : m.p. : 81-82 °C (Hexane). [α]D20 + 43 (c
0.46, CHCl3). 1H NMR (250 MHz; CDCl3): δ : 7.61-7.16 (m, 5H,
H-ar), 4.74 (d, 1H, J1,2 8.67 Hz, H-1), 3.95 (m, 2H, H-3, H-4),
(8) Flowers, H. M.; Levy, A.; Sharon, N. Carbohydr. Res. 1967, 4,
189.
3.76 (m, 2H, H-2, H-5), 1.44 et 1.29 (2s, 6H, CH ), 1.32 (d, 3H,
J6,5 6.25 Hz, H-6), 0.85 (s, 9H, tbutyl), 0.04 and 0.00 (2s, 6H, 2
(9) All new compounds gave satisfactory elemental analysis. NMR
data were in agreement with the proposed structures.
3
CH -Si).
(10) Selected data for 3: m.p. 77°C (Hexane). [α]D20 -12 (c 1, CH2Cl2).
1H NMR (250 MHz, CDCl3): δ : 7.64-7.18 (m, 5H, Ph), 4.59 (d,
1H, J1,2 10.3 Hz, H-1), 4.02-3.93 (m, 2H, H-3, H-4), 3.8 (dq, 1H,
J5,4 2.5 Hz, J5,6 6.25 Hz, H-5), 3.54-3.42 (m, 1H, H-2), 2.38 (d, 1H,
JOH,2 2.21 Hz, OH), 1.36 (d, 3H, H-6), 1.31 and 1.26 (2s, 6H,
CH3).
3
(23) ESR data of 18 at 280K; g value : 2.00295; hyperfine splittings
(G) : a(Hα) 18.45; a(Hβ) 1.40; a(Hγ) 3.75; a(H’γ) 3.75. For a
discussion of ESR coupling constants in carbohydrate radicals,
see: a) Dupuis, J.; Giese, B.; Rügge, D.; Fischer, H.; Korth, H.-G.
Sustmann, R. Angew. Chem. Int. Ed. Engl. 1984, 23, 896.
b) Korth, H.-G.; Sustmann R.; Dupuis, J.; Giese, B. J. Chem.Soc.
Perkin Trans. II 1986,1453.
(11) Wong, G.; Fraser-Reid, B. Can. J. Chem. 1994, 72, 69.
(12) Selected data for 6 : [α]D20 + 32 (c 0.57, CHCl3).1H NMR (400
MHz, CDCl3): δ : 4.75 (d, 1H, J1,2 3 Hz, H-1), 4.35 (dd, 1H, J3’,4’
7.5, J4’,5’3.5 Hz, H-4'), 4.20-4.13 (dq, 1H, J5’,6’6.5, J5’,4’2 Hz, H-5'),
4.08-4.03 (dt, 1H, J1’,2’2.5, J1’,CH2 7 Hz, H-1'), 3.95 (t, 1H, J3,2 = J3,4
9.5 Hz, H-3), 3.51 (t, 1H, J4,5 9.5 Hz, H-4), 3.39 (s, 3H, O-CH3),
(24) Vauzeilles, B.; Cravo, D.; Mallet, J.-M.; Sinaÿ, P. Synlett 1993,
522.
(25) a) Ito, Y.; Ogawa, T. Angew. Chem. Int. Ed. Engl. 1994, 33, 1765.
b) Dan, A.; Ito, Y.; Ogawa, T. J. Org. Chem. 1995, 60, 4680.