104758-89-6

Upstream product

• 3377-92-2 vinyl pivalate 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 
• 3282-30-2 pivaloyl chloride 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 97-30-3 methyl-alpha-D-glucopyranoside 

Downstream Products

• 130130-72-2 methyl (R)-4,6-O-benzylidene-2-O-(2,2-dimethylpropanoyl)-α-D-ribohexopyranosid-3-ulose 
• 112669-91-7 Methyl 4,6-O-benzylidene-2-O-(t-butyldiphenylsilyl)-α-D-ribo-hexopyranosid-3-uloside 
• 50-99-7 D-glucose 
• 112669-93-9 Methyl 4,6-O-benzylidene-3-deoxy-3-C-<(E)-methoxycarbonylmethylene>-2-O-(t-butyldiphenylsilyl)-α-D-ribo-hexopyranoside 
• 130130-73-3 Methyl 4,6-O-benzylidene-3-C-(methoxycarbonylmethylene)-3-deoxy-2-O-pivaloyl-α-D-ribo-hexopyranoside 
• 112669-95-1 Methyl 4,6-O-benzylidene-3-deoxy-3-C-(methoxycarbonylmethylene)-α-D-ribo-hexopyranoside 
• 112669-96-2 Methyl 4,6-O-benzylidene-3-deoxy-3-C-(methoxycarbonylmethylene)-α-D-allopyranoside 
• 112669-98-4 Methyl 4,6-O-benzylidene-3-deoxy-3-(prop-2-yloxycarbonyl)-2,3-butyrolactone-α-D-allopyranoside 
• 112669-97-3 Methyl 4,6-O-benzylidene-3-deoxy-3-(ethoxycarbonyl)-2,3-butyrolacto-α-D-allopyranoside 

Relevant academic research and scientific papers

SELECTIVE LIPASE-CATALYZED ACYLATION OF 4,6-O-BENZYLIDENE-D-GLUCOPYRANOSIDES TO SYNTHETICALLY USEFUL ESTERS

Simple and regioselective lipase-catalyzed acylation of compounds 1 and 4 with synthetically useful esters such as benzoates, chloroacetates, pivaloates and levulinates is described.

Stannous chloride as a low toxicity and extremely cheap catalyst for regio-/site-selective acylation with unusually broad substrate scope

This work reports stannous chloride (SnCl2)-catalyzed regio-/site-selective acylation with unusually broad substrate scope. In addition to 1,2- and 1,3-diols and glycosides containing cis-vicinal diol, the substrate scope also includes glycosides without cis-vicinal diol. For such a substrate scope, usually, only methods using stoichiometric amounts of organotin reagents can lead to the same protection pattern with high selectivities and highly isolated yields (84-97% in most cases). Therefore, SnCl2, as a low toxicity and extremely cheap reagent, should be the best catalyst for regio-/site-selective acylation compared with any previously reported reagents. This journal is

Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins' Bicyclic Sugar Moiety

2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.

The influence of neighboring group participation on the hydrolysis of 2-O-substituted methyl glucopyranosides

Does neighboring group participation actually enhance the reactivity of the anomeric center when the participating group is inherently disarming? To investigate the influence of the neighboring group effect from a 2-O protective group on acidic glycoside hydrolysis, 10 methyl glucosides having different protective groups on O2 have been synthesized and a clear trend between anomeric configuration, participation of the protective group, and the rate of hydrolysis could be observed.

Tetrabutylammonium nitrite - acetic anhydride system, tetrabutylammonium nitrite, tetrabutylammonium acetate, and cesium acetate - 18-crown-6 for efficient unmasking of alkyl N-phenylcarbamates

Novel unmasking procedures for alkyl N-phenylcarbamates are established by the use of a tetrabutylammonium nitrite (Bu4NNO2) - acetic anhydride system, Bu4NNO2, Bu4NOAc, and CsOAc 18-crown-6 towards variously functionalized sugar derivatives.

The 'Off-template' Problem: Towards a General Solution

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.