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New strategies for the synthesis and functionalization of aliphatic amines 10.17863/CAM.35257 Trowbridge, Aaron Daniel Gaunt, Matthew J. The invention of catalytic processes that convert feedstock chemicals into pharmacologically-privileged amines is a landmark challenge in organic synthesis. This thesis describes the development of three novel transition-metal catalyzed processes for the synthesis of alkylamines that attempts to meet this challenge. The first Pd-catalyzed methylene β-C−H carbonylation of alkylamines to form substituted β-lactams is reported. Through the synergistic use of a Pd-catalyst and Xanpthos ligand, secondary amines underwent exclusive methylene β-C−H activation in high yields and diastereoselectivities. Subsequently, the development of a remarkably selective methylene β-C−H carbonylation of α-tertiary amines (ATAs), is detailed. This methodology enables the C−H carbonylation of methylene C−H bonds over traditionally more reactive methyl and C(sp2)−H bonds. Importantly, a range of functional groups previously incompatible with C−H technologies were tolerated in good yields. Finally, the development of a novel multicomponent synthesis of tertiary amines is described. The novel photocatalytic single-electron reduction of alkyl iminium ions furnishes -amino radicals that engage alkenes forming a new C–C bond. The reaction exhibits broad functional group tolerance and enables the synthesis of amines not readily accessible by existing methods. University of Cambridge 2019-01-26 Thesis Doctoral Doctor of Philosophy (PhD) en Herchel Smith Scholarship https://www.repository.cam.ac.uk/handle/1810/287941 https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/449c3566-4ba1-4be8-a56c-f55b2a5edd18/download 009f6173c5c4048f0033c9e3859ad41c https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/669bddf1-9a50-4b66-998a-c1eb12942c43/download 87eda9de84448d1f82354d60eee3eb5f https://www.rioxx.net/licenses/all-rights-reserved/ C-H activation transition-metal catalysis amines photocatalysis multicomponent alkylamines hydroaminoalkylation carbonylation palladium lactam