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Reactivity, Selectivity, and Synthesis of 4‐ C ‐Silylated Glycosyl Donors and 4‐Deoxy Analogues
Author(s) -
Jæger Pedersen Martin,
Pedersen Christian Marcus
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202009209
Subject(s) - reactivity (psychology) , chemistry , glycosyl , selectivity , anomer , glycosylation , silylation , glycosyl donor , glycoside , stereochemistry , glucoside , carbohydrate synthesis , carbohydrate , organic chemistry , catalysis , biochemistry , medicine , alternative medicine , pathology
A method for introducing dimethylphenylsilyl at the 4‐position in carbohydrates has been developed. Two C‐silylated glycosyl donors were prepared via levoglucosenone, starting from cellulose. The glycosylation properties were studied using three glucoside acceptors, a 3‐OH, 4‐OH, and 6‐OH. Compared with the 4‐deoxy variant, it was found that the anomeric selectivity was influenced more by the C‐2 substituents orientation than the silyl in the 4‐position. In general, the reactivity of these donors was higher than the corresponding 4‐deoxy‐analogue, albeit a competition experiment showed that the introduction of a C−Si increases the relative reactivity by a modest factor of around two.