Peptidyl Glycosyl Thiols and Disulfides for Enantioselective Hydrogen Atom Transfer (HAT) and Thiyl Radical Catalysis

A novel class of peptidyl glycosyl disulfide and thiol
catalysts
is developed. The thiols are found to catalyze enantioselective olefin
hydrosilylation up to 5:95 er. The disulfide catalysts are competent
in an enantioselective thiyl-catalyzed cycloaddition reaction, yielding
product with complementary selectivity to that previously reported
with cystine-based catalysts. The modular nature of these catalysts
provides new opportunities for asymmetric thiyl and thiol HAT catalysis.