Nickel-catalyzed cross-couplings of unactivated secondary and tertiary alkyl halides and photoinduced copper-mediated asymmetric C-N cross-couplings
Author(s)Zultanski, Susan L. (Susan Lyn)
Massachusetts Institute of Technology. Department of Chemistry.
Gregory C. Fu.
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Chapter 1 describes the development of two nickel-catalyzed Suzuki cross-coupling methodologies that employ alkyl halides as electrophiles. In Section 1.1, asymmetric [gamma]-alkylation relative to a carbonyl group is achieved via the stereoconvergent cross-coupling of racemic secondary [gamma]-chloroamides with primary alkylboranes. Section 1.2 describes the first Suzuki carbon-carbon bond-forming reaction using tertiary alkyl halides as electrophiles; specifically, unactivated tertiary alkyl bromides are cross-coupled with arylboranes. Chapter 2 describes the establishment of photoinduced asymmetric copper-mediated C-N Ullmann-type coupling processes between racemic secondary alkyl halides and N-heterocycles. Preliminary yields and enantioselectivities for a reaction between secondary benzylic halides and carbazoles, with the use of a monodentate chiral phosphine ligand, are presented. The methodology is then extended to secondary [alpha]-haloamides, including [alpha]-halolactams, which are found to afford very promising yields and enantioselectivities.
Thesis (Ph. D. in Organic Chemistry)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013.Cataloged from PDF version of thesis. Vita.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Department of Chemistry.
Massachusetts Institute of Technology