Open AccessStereoretentive Intramolecular Glycosyl Cross-Coupling: Development, Scope, and Kinetic Isotope Effect Study
Author(s) -
Duk Yi,
Feng Zhu,
M Walczak
Publication year - 2018
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.8b01927
Subject(s) - chemistry , intramolecular force , stille reaction , steric effects , nucleophile , aryl , phosphine , anomer , intermolecular force , ligand (biochemistry) , computational chemistry , stereochemistry , combinatorial chemistry , alkyl , catalysis , organic chemistry , molecule , biochemistry , receptor
A series of cyclic C-glycosides were synthesized using the palladium-catalyzed stereoretentive intramolecular glycosylation of aryl iodides by employing a bulky phosphine ligand. A variety of functional groups are tolerated in the reaction, and enantioenriched anomeric nucleophiles could be coupled without erosion of optical purity. This study offers a unified method to access both cis- and trans-fused rings by capitalizing on the stereoretentive nature of the Stille reaction. In addition, competition experiments for intermolecular and intramolecular cross-couplings revealed secondary KIEs of 1.43 and 0.81, respectively, suggesting a profoundly different steric congestion at the transition state.