Remote Desymmetrization at Near-Nanometer Group Separation Catalyzed by a Miniaturized Enzyme Mimic

摘要

Among the most challenging problems for enantioselective catalysis is that of remote asymmetric induction.For example,remote desymmetrizations of meso compounds require bond formation (or cleavage) at a site within a substrate that is distal from both a pro-stereogenic structural element and the competing enantiotopic functional group.Problems of this type are often handled through an intramolecular relay of chiral information through the substrate.When catalytic bond formation is required,across a truly substantial distance,enzymes are often employed since their macromolecular architecture presents the potential for enantioselective recognition and functionalization over a substantial vector.Selective C-H bond oxidations distal from functionality and stereogenic centers provide some of the most dramatic examples.When small molecule catalysts are applied to desymmetrizations,oftentimes even striking cases involve relatively short distances between enantiotopic groups.