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.
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.
Bhattacharya
Rahul
R
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India.
Kesharwani
Manoj K
MK
Manna
Chinmoy
C
Ganguly
Bishwajit
B
Suresh
Cheravakattu G
CG
Pathak
Tanmaya
T
D000588:Amines / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006027:Glycosides / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*
D000588:Amines; D006027:Glycosides; D013450:Sulfones; C009873:divinyl sulfone