Metal-mediated oxidation reactions play an important role in biological processes and in abiological reactions used in organic synthesis. The function of a large proportion of these reactions is the transfer of groups containing heteroatoms such as nitrogen, oxygen, phosphorus and sulfur to organic molecules. Many of these processes have been postulated to proceed via metal complexes that contain reactive metal-heteroatom multiple bonds. However, exploration of the chemistry of these functionalities, extending and applying their reactions to transformations useful in organic synthesis, and understanding the mechanisms of their reactions, lag substantially behind what is known about analogous processes involving metal-carbon multiple bonds (carbene complexes). As a result, there is a need for development of new chemistry based on isolable complexes that bear metal-heteroatom multiple bonds. ? ? The overall goal of this proposal is the development of systematic methods for the synthesis of complexes containing metal-heteroatom multiple bonds, the development of new stoichiometric and catalytic reactions in which these bonds play a central role that can be applicable to organic synthesis, and the study of the scope and mechanisms of these reactions. A significant part of the project will be devoted to the synthesis of chiral, enantioresolved complexes that can be used in the development of stereoselective transformations leading to enantioenriched organic compounds with new bonds between carbon and heteroatoms. Specific targets for the proposed grant period will be the development of (1) stereoselective, catalytic and stoichiometric carboamination of alkynes; (2) catalytic diimination of unsaturated substrates; (3) highly regio- and stereoselective allylic substitutions of allyl halides and ethers; (4) methods for desymmetrization of meso-epoxides; (5) reactive and enantioselective catalysts for the hydroamination of alkenes; (6) catalytic hydrophosphination of alkenes and alkynes; (7) exploration of the addition of organic C-H bonds to metal-heteroatom multiple bonds. ? ?
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