73014-31-0

Upstream product

• 7677-24-9 trimethylsilyl cyanide 
• 108-24-7 acetic anhydride 
• 592-04-1 mercury(II) cyanide 
• 3068-32-4 1-bromo-1-deoxy-2,3,4,6-tetra-O-acetyl-a-D-galactopyranoside 
• 52443-08-0 3,4,6-tri-O-acetyl-1,2-O-<(exo and endo)-1-cyanoethylidene>-α-D-galactopyranose 
• 83497-42-1 2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl cyanide 

Downstream Products

• 83497-42-1 2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl cyanide 

Relevant academic research and scientific papers

Efficient stereocontrolled synthesis of C-glycosides using glycosyl donors substituted by propane 1,3-diyl phosphate as the leaving group

α- and β-Glycosyl cyanides, per-O-acetyl-1,2-O-1-cyanoethylidenes and C-allyl glycopyranosides were efficiently prepared by treatment of 2,3,4-tri-O-acetyl-α,β-L-rhamno-, L-fuco- and 2,3,4,6-tetra-O-acetyl-α,β-D-galactopyranosyl propane-1,3-diyl phosphate

Efficient Syntheses of β-Cyanosugars Using Glycosyl Iodides Derived from Per-O-silylated Mono- and Disaccharides

Reported herein is a general method for the efficient syntheses of a variety of β-cyano glycosides through the activation of per-O-trimethylsilyl glycosides with TMSI to form α-glycosyl iodides, which undergo SN2-type displacement when treated with tetrabutylammonium cyanide. The cyanoglycosides were reduced under mild conditions using NaBH4 in the presence of catalytic CoCl2(H2O)6 in THF/H2O to give the corresponding aminomethyl glycosides.

Preparation of 2,6-Anhydro-3-deoxyhept-(or hex-)2-enononitriles (1-Cyanoglycals) from 1-Bromo-D-glycosyl Cyanides with Zinc under Aprotic Conditions

Acetylated 1-bromo-D-glycosyl cyanides 1 - 5 react with zinc dust in acetic acid, acetic acid/water, or 2-propanol to give mixtures of acetylated 1-cyanoglycals 6-9 and anomeric pairs of glycosyl cyanides 10-14.Reaction of 1-5 in refluxing benzene in the presence of one equivalent of triethylamine or especially pyridine predominantly leads to the formation of 1-cyanoglycals.

Improved preparations of some per-O-acetylated aldohexopyranosyl cyanides.

3,4,6-Tri-O-acetyl-1,2-O-[1-(exo-, endo-cyano)ethylidene]-alpha-D- galacto- (1a/b), -alpha-D-gluco- (2a/b), and -beta-D-manno-pyranose (3a/b) were stereoselectively isomerized to the corresponding per-O-acetylated 1,2-trans-aldohexopyranosyl cyanides in 75, 16, and 62% yield, respectively, by treatment with boron trifluoride etherate in dry nitromethane. The corresponding per-O-acetylated 1,2-cis-aldohexopyranosyl cyanides were obtained concurrently in respective yields of 1.9, 0.9, and 4.8%. The per-O-acetylaldohexopyranosyl cyanide products were found stable to the reaction conditions and were readily isolated following completion of the rearrangement. It had previously been proved that reaction of 2,3,4,6-tetra-O-acetyl-alpha-D-manno- and -gluco-pyranosyl bromide with mercuric cyanide in nitromethane generates, in the ratio of approximately 1:1, the desired 1,2-trans-glycosyl cyanides and the corresponding 1,2-O-(1-cyanoethylidene) isomers (3a/b and 2a/b, respectively). Treatment of these reaction-mixtures with boron trifluoride etherate in nitromethane effected the rearrangement of 3a/b and 2a/b, thereby facilitating the isolation, and increasing the overall yields, of the per-O-acetylated 1,2-trans-D-manno- and -gluco-pyranosyl cyanides (58 and 30% total yield, respectively) relative to the earlier procedures. The boron trifluoride etherate-mediated reaction of per-O-acetyl-alpha- and -beta-D-galacto-, -alpha- and -beta-D-gluco-, -alpha-D-manno-, and -2-deoxy-2-phthalimido-beta-D-gluco-pyranoses with trimethylsilyl cyanide in nitromethane was also investigated. This reaction provides a "one-flask" synthesis of the corresponding per-O-acetylated 1,2-trans-aldohexopyranosyl cyanides in which 1,2-O-(1-cyanoethylidene) derivatives are isomerized in situ. Finally, improved preparations of the (not readily accessible) per-O-acetylated 1,2-cis-D-manno- and -gluco-pyranosyl cyanides are described. Thus, 2,3,4,6-tetra-O-acetyl-alpha- and -beta-D-mannopyranosyl cyanide (48 and 16% total yield, respectively) and -alpha- and -beta-D-glucopyranosyl cyanide (12 and 39% total yield, respectively) were synthesized by fusion of the corresponding alpha-D-glycosyl bromides with mercuric cyanide.

PREPARATION OF 1,2-CIS-GLYCOSYL CYANIDES BY THE STEREOSELECTIVE REDUCTION OF ACETYLATED 1-BROMO-D-GLYCOSYL CYANIDES

Reductive dehalogenation of acetylated 1-bromo-D-glycosyl cyanides with tri-n-butyltin hydride favours the formation of 1,2-trans-glycosyl cyanides, while reactions with zinc-acetic acid, zinc-isopropanol, and sodium borohydride give 1,2-cis-glycosyl cyanides as the major product.

Synthesis and characterization of some anomeric pairs of per-O-acetylated aldohexopyranosyl cyanides (per-O-acetylated 2,6-anhydroheptononitriles). On the reaction of per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane.

The synthesis and characterization of the anomeric pairs of the per-O-acetylaldohexopyranosyl cyanides of D-galactose, L-fucose, D-glucose, and D-mannose, as well as of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranosyl cyanide, are described. Cyanation of the readily available, per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane, and subsequent purification, gave the corresponding, crystalline glycosyl cyanides with a high degree of 1,2-trans stereoselectivity. Thus, per-O-acetylated aldohexopyranosyl cyanides of the 1,2-trans configuration were obtained in yields ranging from 20 to 79%, whereas the corresponding 1,2-cis anomers were obtained in yields of less than or equal to 8.4%, the ratios of the 1,2-trans:1,2-cis anomers so prepared being greater than or equal to 8.5:1. The principal by-products of these irreversible, cyanation reactions were the per-O-acetylated 1,2-O-[1-(exo- and endo-cyano)ethylidene]aldohexopyranoses, obtained in yields of up to 40%. The structural assignments of the per-O-acetylaldohexopyranosyl cyanides were unequivocally established by elemental analysis, chemical transformation, vibrational spectroscopy, and 13C- and 1H-nuclear magnetic resonance spectroscopy. Correlations between the physical properties and the anomeric configurations of these C-aldohexopyranosyl compounds are described.