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Title: Enantioselective Hydrogen Atom Transfer with Carbohydrate and Peptide Derived Thiol Catalysts
Both metal and non-metal catalyzed hydrogen atom transfer (HAT) reactions have become enabling methods garnering significant attention in recent years for reductive transformations. Herein, we describe the mechanistic investigation of olefin hydrogenation by Fe/thiol cooperative hydrogen atom transfer (cHAT) utilizing kinetic analysis, spectroscopy, and computations. The insights from this study enabled the observation of unambiguous enantioselectivity up to 80:20 enantiomeric ratio using chiral thiols—the first demonstration of asymmetric hydrogenation via iron-catalyzed metal hydrogen atom transfer (mHAT). We further report the design and synthesis of peptidyl glycosyl thiols—a novel class of chiral thiol catalyst. These catalysts proved competent in olefin hydrogenation and hydrosilylation and yielded products of hydrosilylation in high enantioselectivity.