An Experimental and Theoretical Study on the Remarkable Influence of Protecting Groups on the Selectivity of Addition of Amines to Vinyl Sulfone-Modified Hex-2-enopyranosides

Autor:	Manoj K. Kesharwani, C.G. Suresh, Bishwajit Ganguly, Tanmaya Pathak, Chinmoy Manna, Rahul Bhattacharya
Rok vydání:	2009
Předmět:	Reaction mechanism Molecular Structure Chemistry Concerted reaction Organic Chemistry Stereoisomerism Activation energy Crystallography X-Ray Quantum chemistry Sulfone chemistry.chemical_compound Michael reaction Organic chemistry Glycosides Sulfones Amines Selectivity Protecting group
Zdroj:	The Journal of Organic Chemistry. 75:303-314
ISSN:	1520-6904 0022-3263
Popis:	Although phenylmethylene-protected vinyl sulfone-modified carbohydrate 2alpha reacts with both primary and secondary amines in Michael fashion to afford aminated products, only primary amines react with the dibenzyl-protected 3alpha, 6-O-trityl-protected 4alpha, and unprotected 5alpha, highlighting for the first time the remarkable influence of protecting groups on the reaction patterns of vinyl sulfone-modified carbohydrates. The quantum chemical calculations suggest that the Michael addition of amines and proton transfer to vinyl sulfone-modified carbohydrates 2alpha and 5alpha are possible via relay process in a concerted mechanism. These calculations reveal that the addition of primary amines to vinyl sulfone-modified carbohydrate is preferential due to the low activation energy barriers, whereas the addition of secondary amines has relatively higher activation energy barriers. The theoretical conclusions are in line with the experimental observations.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::290a1215caf36ef18451ebae8b69c2f2 https://doi.org/10.1021/jo902046g Zobrazit plný text záznamu