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.