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Unsaturated Nitriles: Stereoselective Annulations And Alkylations, Zhiyu Zhang

Electronic Theses and Dissertations

N-metallated nitriles are fundamental intermediate that have been used to generate new C-C bonds for over a century. C-metallated nitriles are new but equally important intermediates in being able to deliver complementary stereoselectivity. C-magnesiated nitriles are directly generated from chelation-controlled conjugated addition and can successfully furnish complete stereocontrol during installation of three new stereocenters (Section II-1).

The recent development of chiral organometallics has identified a remarkable series of electrophile-dependent alkylations that are significantly impacting organic synthesis. C-magnesiated nitriles from chelation-controlled conjugated addition are chiral nucleophiles that alkylate an array of electrophiles with retentive or invertive alkylation depending on the electrophiles. …