Our group has sought the functionalization of C-H and C=C bonds catalyzed by transition-metal complexes with control of site-selectivity, regioselectivity and enantioselectivity. We have reported widely practiced functionalizations of aromatic C-H bonds with boron reagents and recently discovered catalysts that functionalize primary alkyl C-H bonds under practical conditions. In parallel, we have sought to create artificial metalloenzymes that contain catalysts from the laboratory as the active site for regioselective and stereoselective functionalizations of C-H and C=C bonds. This lecture will present selected examples from and mechanistic analysis of our functionalizations of C-H bonds at primary, secondary, and tertiary positions with small-molecule catalysts, along with the creation of artificial metalloenzymes that catalyze organometallic reactions within whole cells and within biosynthetic pathways of these cells to produce unnatural products.
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