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Carbon-carbon bond formation : reactions of alkenyltrimethylstannanes mediated by copper(I) salts Yee, James Gee Ken

Abstract

The work in this thesis is described in two sections. In the first section, the conjugate addition of alkenyltrirnethylstannane functions to α,β-alkynic esters mediated by copper(I) chloride are discussed. An experimental protocol employing copper(I) chloride and acetic acid in N,N-dimethylforaiamide was developed to effect the stereoselective conversion of the precursors 80 and 178-185 into the monocyclic compounds 81 and bicyclic compounds 186-193, respectively. The intramolecular copper(I)-mediated conjugate addition of aryltrimethyl stannane functions to α,β -alkynic esters was also explored. A variety of bicyclic compounds of general structure 89 that each incorporate an aromatic ring were prepared by this method. α,β -Alkynic aldehydes and α,β -alkynic ketones were shown to function as viable Michael acceptors in the conversion of 233 and 235 into 236-237 and 238-239, respectively. The catalytic nature of the copper(I) chloride in the reaction was also demonstrated. In the second part of this thesis, the copper(I) chloride-mediated oxidative coupling of alkenyltrimethylstannane and aryltrimethylstannane functions is discussed. The intermolecular homocoupling of β-trirnethylstannyl- α,β -unsaturated ketones 100 produced the structurally unusual diketones 101 upon the treatment of the precursors with copper(I) chloride. The synthesis of the 5-, 6-, and 7-membered ring compounds 105, 107, 109, 111, and 113 from the precursors 104, 106, 108, 110, and 112, respectively, was accomplished by use of the intramolecular variant of the coupling reaction. The scope of the methodology was extended to include the formation of 9-membered and 10-membered ring compounds of general structure 115.

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