Copper(II)-Catalyzed and Promoted Alkene and Allene Difuntionalization: Carboamination, Aminooxygenation, and Dioxygenation
Casavant, Barbara J.
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Functionalized nitrogen and oxygen heterocycles are an abundant class of compounds found throughout nature and the chemical industry. Their frequent use in biologically active molecules and as ligands for the metals involved in asymmetric catalysis has made these compounds attractive synthetic targets. The research that follows describes my contributions to alkene and allene difunctionalization catalyzed by copper(II) in the preparation of functionalized pyrrolidines and tetrahydrofurans. In chapter 1 a brief review of the current carboaminaiton literature is given before a new copper(II)-catalyzed carboamination reaction that gives 6-Azabicyclo[3.2.1]octanes is discussed. These bridged bicyclic products are formed in a single step from N-sulfonyl-2-aryl-4-pentenamines. Over a range of sulfonyl protecting groups and aryl substituents, the resulting heterocycles were generally formed in good yields with good to excellent enantiomeric excess (ee). Both substrate desymmeterization and reaction scalability are also discussed. In chapter 2, allene difunctionalization is explored and copper(II)-promoted aminooxygenation and dioxygenation is discussed. These new reactions provide heterocycle-functionalized vinyl carboxylate esters in a single step from allenols and allenylsulfonamides. Over a range of substrates, the aminooxygenation and dioxygenation transformations afford the functionalized vinyl carboxylate ester products in generally moderate to good yields. Both reaction types were shown to be diastereoselective and product utility was briefly demonstrated.