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Catalytic and Atom‐Economic Glycosylation using Glycosyl Formates and Cheap Metal Salts
Author(s) -
Yang Liang,
Hammelev Christian H.,
Pedersen Christian M.
Publication year - 2020
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.202000733
Subject(s) - chemistry , catalysis , glycosyl , formic acid , hemiacetal , glycosylation , organic chemistry , yield (engineering) , combinatorial chemistry , reagent , biochemistry , materials science , metallurgy
Benzylated glycosyl formates have been synthesized in one step from the corresponding hemiacetal or orthoester with formic acid as the sole reagent. The glycosyl formates are used as glycosyl donors under catalytic conditions with cheap metal catalysts based on iron or bismuth. A 13 C NMR spectroscopic method is developed and evaluated for screening reactions conditions, giving precise information on the selectivity, yield, and byproducts formed. The major side reaction is transesterification, which gives the formylated acceptor and regenerates the hemiacetal. By using this approach, catalyst loadings and solvents are optimized and the scope of the glycosylation is evaluated for a variety of glycosyl donors and acceptors. A proof of concept for a traceless glycosylation, utilizing a dual‐purpose iron catalyst that catalyzes both glycosylation and dehydrogenation of formic acid, is also provided.