Open AccessStereospecific Furanosylations Catalyzed by Bis-thiourea Hydrogen-Bond Donors
Author(s) -
Andrew Beckmann Mayfield,
Jan B. Metternich,
Adam H. Trotta,
Eric N. Jacobsen
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c00335
Subject(s) - chemistry , stereospecificity , anomer , thiourea , stereoselectivity , catalysis , stereochemistry , hydrogen bond , selectivity , medicinal chemistry , organic chemistry , molecule
We report a new method for stereoselective O -furanosylation reactions promoted by a precisely tailored bis-thiourea hydrogen-bond-donor catalyst. Furanosyl donors outfitted with an anomeric dialkylphosphate leaving group undergo substitution with high anomeric selectivity, providing access to the challenging 1,2- cis substitution pattern with a range of alcohol acceptors. A variety of stereochemically distinct, benzyl-protected glycosyl donors were engaged successfully as substrates. Mechanistic studies support a stereospecific mechanism in which rate-determining substitution occurs from a catalyst-donor resting-state complex.