78342-32-2Relevant academic research and scientific papers
Highly Stereoselective Introduction of Fluorine-Containing Methyl Groups at 2 Position of D-Glucose
Hiraoka, Shuichi,Yamazaki, Takashi,Kitazume, Tomoya
, p. 669 - 670 (2007/10/03)
Highly stereoselective introduction of fluorine-containing methyl groups at the 2 position of methyl glucoside was attained by use of the difluoromethylene derivative as a key intermediate via hydrogenation of exo- and endo-olefins, whose diastereofacial selectivity was considered to be governed by the anomeric methoxy group.
Stereospecific synthesis of branched-chain sugars by a novel aldol-type cyclocondensation
Perez-Perez, Maria-Jesus,Camarasa, Maria-Jose,Diaz-Ortiz, Angel,Felix, Ana San,Heras, Federico G. de las
, p. 399 - 411 (2007/10/02)
A procedure for the preparation of branched-chain sugars having highly functionalised C-branches is reported.Reaction of furanos-3-uloses, pyranos-3-uloses, or pyranos-2-uloses with sodium cyanide followed by mesylation of the corresponding cyanohydrin af
The 'Off-template' Problem: Towards a General Solution
Rashid, Abdul,Taylor, G. Mark,Wood, William W.,Alker, David
, p. 1289 - 1296 (2007/10/02)
Wittig reaction of the t-butyldimethylsilylated C-3 ketone methyl 4,6-O-benzylidene-2-O-(t-butyldimethylsilyl)-α-D-ribo-hexopyranosid-3-uloside leads exclusively to C-2 alkenes, providing an efficient synthesis of these potentially useful intermediates.Alternatively, the corresponding t-butyldiphenylsilyl ether, prepared with complete regiospecificity from methyl 4,6-O-benzylidene-α-D-glucopyranoside, gives a C-3 alkene on oxidation and Wittig reaction.Deprotection, hydrogenation and cyclization of this product leads to the cis-fused butyrolactone, methyl 4,6-O-benzylidene-3-deoxy-3-(ethoxycarbonyl)-2,3-butyrolactone-α-D-allopyranoside, which is alkylated stereospecifically to give methyl 4,6-O-benzylidene-3-deoxy-3-(prop-2-yloxycarbonyl)-2,3-butyrolacto-α-D-allopyranoside.This procedure provides a general solution of the 'off-template' problem of carbohydrate-based natural product synthesis.
THE "OFF-TEMPLATE" PROBLEM: SYNTHESIS AND ALKYLATION OF A FUSED-BUTYROLACTONE FROM D-GLUCOSE
Wood, William W.,Rashid, Abdul
, p. 1933 - 1936 (2007/10/02)
The synthesis of a fused-butyrolactone from D-glucose and its stereospecific alkylation in an off-template position is described, together with an unusual silyl protecting group migration.
Out-of-Ring Claisen Rearrangement are Highly Stereoselective in Pyranoses: Routes to gem-Dialkylated Sugars
Tulshian, Deen Bandhu,Tsang, Raymond,Fraser-Reid, Bert
, p. 2347 - 2355 (2007/10/02)
The Claisen rearrangement has been evaluated as a means for stereoselective creation of functionalized geminal substituents at C-2 and C-3 of hexopyrano systems.C-2 and C-3 keto sugars react with Wittig reagents to give α,β-unsaturated esters, one geometric isomer being obtained in each case.Reduction of the ester and trans vinylation with ethyl vinyl ether leads to allyl vinyl ethers wich are thermolysed in refluxing benzonitrile.The oxy-Cope rearrengement proceeds with complete stereoselectivity, the folding pattern being always from the β-face of the pyranose ring.Thus, the acetaldehyde moiety ends up axially oriented at C-2 and equatorially oriented at C-3.These stereochemical results are not affected by neighboring oxygen substituents nor by the presence or absence of an anomeric alkoxyl functionality.
Highly Stereoselective Routes to Functionalized Geminal Alkyl Derivatives of Carbohydrates
Fraser-Reid, Bert,Tsang, Raymond,Tulshian, Deen Bundhu,Sun, King Mo
, p. 3764 - 3767 (2007/10/02)
2-, 3-, and 4-Keto derivatives of some α-D-hexopyranosides react with Ph3P=CHCOOEt to give a single geometric isomer in each case, which is readily converted into an allyl vinyl ether.Claisen rearrangements of the latter proceed with high stereoselectivit
