Synthese D'Azotures et de Benzoates de Glycosyle a Partir de Sulfites Cycliques Enc C-1, C-2

Abstract

The reaction of sugars bearing a cyclic sulfite group on C-l,C-2 with azide or benzoate ions, is strereoselective and gives trans-1,2 glycosyl azides or glycosyl benzoates with a free hydroxyle at C-2. The reaction is performed under mild conditions and gives excellent yields of glycosyl derivatives.

Regioselective azidotrimethylsilylation of carbohydrates and applications thereof

“…4, 128.5, 128.4, 128.3, 127.8, 127.3, 111.9, 105.0, 81.4, 81.2, 80.6, 71.6, 68.5, 55.1, 26.8, 26.3 3.45 (d,J = 12.8 Hz,1H,3.25 (dd,J = 11.1,12.8 Hz,1H, H-6a/b), 1.39 (s, 3H), 1.18 (s, 3H), 0.032 (s, 9H). 13 C NMR (50 MHz, CDCl 3 ), δ; 137.4, 128.5, 128.4, 127.8, 127.3, 127.2, 111.9, 105.0, 81.7, 81.3, 80.6, 71.6, 68.5, 55.1, 26.8, 26.3, 0.4 (3C) C,56.00;H,7.17;N,10.31;Found C,55.92;H,7.02;N,10.21. -glucofuranose (3a).…”

“…1 H NMR (500 MHz, CDCl 3 ), δ; 5.67 (d, J = 3.7 Hz, 1H), 4.40 (d, J = 3.7 Hz, 1H), 3.94 (dd, J = 2.7, 6.1 Hz, 1H), 3.96-3.94 (m, 1H), 3.67 (d, J = 2.7 Hz, 1H), 3.52 (dd, J = 1.9, 5.1 Hz, 1H), 3.39 (dd, J = 2.3, 10.4 Hz, 1H), 3.29 (dd, J = 1.9, 5.1 Hz, 1H, H-6a/b), 3.17 (dd, J = 5.1, 7.6 Hz, 1H, H-6a/b), 1.32 (s, 3H), 1.14 (s, 3H), 1.05 (t, J = 6.9 Hz, 3H), 0.006 (s, 9H). 13 C NMR (50 MHz, CDCl 3 ), δ; 111. 6, 104.6, 81.0, 80.9, 80.0, 66.8, 64.8, 53.0, 26.4, 26.1, 14.6, 0.21 (3C).…”

“…6 Hz,1H),4.23 (dd,J = 2.4,5.6 Hz,1H),4.17 (dd,J = 2.8,8.8 Hz,1H),4.10 (dd,J = 2.8,4.8 Hz,1H),4.08 (d,J = 3.2 Hz,2H),3.55 (dd,J = 2.8,12.8 Hz,1H,3.34 (dd,J = 4.8,12.8 Hz,1H,2.48 (s,1H), 1.49 (s, 3H), 1.30 (s, 3H), 0.178 (s, 9H). 13 C NMR (50 MHz, CDCl 3 ), δ; 111. 5, 104.4, 80.4, 80.2, 80.0, 78.2, 75.4, 67.8, 56.6, 54.4, 26.2, 25.8, −0.47 (3C).…”

“…[α] 20 D = -68.9 (c, 1.0, CHCl 3 ). 1 H NMR (500 MHz, CDCl 3 ), δ; 7.32-7.24 (m, 10H), 4.71 (s, 1H), 4.64 (d, J =11.2 Hz, 1H), 4.62(d, J =11.9 Hz, 1H), 4.55 (s, 1H), 4.52 (d, J =11.4 Hz, 1H), 4.37 (dd, J = 4.4, 8.6 Hz, 1H), 4.17 (s, 1H), 4.04 (m, 1H), 3.98 (d, J = 4.0 Hz, 1H), 3.71 (dd, J =2.4, 100 13.6 Hz, 1H, H-6a/b), 3.43 (dd, J = 4.6, 13.6 Hz, 1H, H-6a/b), 3.38 (s, 3H, -OCH 3 ), 0.09 (s, 9H) 13. C NMR (125 MHz, CDCl 3 ) δ, 138.1, 137.8, 128.5, 128.4, 128.3, 128.2, 128.1, 128.0, 127.9, 127.86, 127.84, 127.7, 110.8, 83.0, 81.5, 79.0, 76.4, 72.4, 72.1, 56.2, 52.1, 0.00 (3C).…”

“…10 In carbohydrate chemistry, several methods of the synthesis of glycosyl azides have been explored, i.e. reactions of glycosyl halides with metal azides or tetramethylguanidinium azide under homogeneous conditions or by using phase transfer catalysts; 11 reactions of glycosyl esters with trimethylsilyl azide in the presence of a Lewis acid catalyst; 12 reacting cyclic 1,2-sulfite sugar derivatives 13 and thiocarbonate ring opening with NaN 3 . 14 The selective azidation of the terminal hydroxyl group in monosaccharides for the synthesis of 6-deoxy-6-azido-2,3,4-tri-O-trimethylsilyl ethers involves multiple reaction steps i.e.…”