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TBTU, O-(benzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium tetrafluoborate; NEM, N-ethylmorpholine. See: Knorr, R.; Trzeciak, A.; Bannwarth, W.; Gillessen, D. Tetrahedron Lett. 1989, 30, 1927.
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4) and carbon-carbon double bond (diimide), and finally Barton-McCombie dehydroxylation.
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The general procedures for the synthesis of α- and β-linked ethynyl glycopyranosides (glucose, galactose, mannose, and the corresponding 2-acetamido-2-deoxy derivatives) were described. The β-D-isomers were obtained by addition of cerium TMS-acetylide to the sugar lactones, reduction of the corresponding ketols, and desilylation; the α-D-isomers were prepared by C-glycosidation of anomeric sugar acetates using a mixed Sn-Si bis-metalated acetylene acceptor followed by desilylation.
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This reaction has been applied to various sugar lactones and constitutes the initial step of the thiazole-based synthesis of formyl C-glycosides, see ref 29
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Other examples of this synthetic route by the use of benzothiazole as the formyl group equivalent have been demonstrated in the authors laboratory. The use of the benzothiazole ring avoids some side reactions that have been occasionally observed between the azido group and the intermediates that are formed in the unmasking sequence of the thiazole ring to the formyl group.
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Dominique, R.1
Liu, B.2
Das, S.K.3
Roy, R.4
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