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Title: Cross-Coupling of Native sp3 C–H Bonds with Vinyl Halides Through the Triple Merger of Nickel, Photoredox, and HAT Catalysis
Authors: Zhang, Tiancheng
Advisors: MacMillan, David W.
Department: Chemistry
Class Year: 2016
Abstract: This work describes a novel and general method for the selective sp\(^{3}\) C–H vinylation of a variety of amines and ethers through the triple merger of nickel, photoredox, and HAT catalysis. This use of unactivated sp\(^{3}\) C–H bonds as nucleophilic coupling partners represents a new paradigm in transition-metal-catalyzed cross-coupling, which is predominantly reliant on prior substrate activation and functionalization; by exploiting native molecule functionality instead, this method has the potential to significantly streamline synthetic sequences towards target molecules. Available under mild conditions, this transformation generates good yields as well as excellent selectivity for the functionalization of α-amino and α-oxy sp\(^{3}\) C–H bonds, and is one of the first examples of a general sp\(^{3}\) C–H vinylation to be described within the literature. Efforts have been taken towards demonstrating both the efficiency of this transformation as well as the versatility and generality of the procedure in tolerating a range of vinyl halides as well as a wide variety of cyclic and acyclic amines and ethers. More importantly, this transformation demonstrates significant future promise, with the potential to be employed in dual cross-coupling reactions, or used for batch-scale synthesis, or further developed into an asymmetric transformation to deliver enantioenriched vinylation products. In conclusion, the sp\(^{3}\) C–H vinylation reaction described by this work provides a valuable and efficient synthetic method that provides access to a wide range of desirable and potentially complex vinylation products.
Extent: 115 pages
Type of Material: Princeton University Senior Theses
Language: en_US
Appears in Collections:Chemistry, 1926-2016

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