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Please use this identifier to cite or link to this item: http://arks.princeton.edu/ark:/88435/dsp012v23vx76s
Title: DIVERSIFYING THE SYNTHETIC TOOLBOX VIA PHOTOREDOX REACTION DEVELOPMENT AND GENERALIZATION
Authors: Prieto Kullmer, Cesar Nicolas
Advisors: MacMillan, David W. C.
Contributors: Chemistry Department
Keywords: catalysis
cross-coupling
generality
photoredox
Subjects: Organic chemistry
Issue Date: 2024
Publisher: Princeton, NJ : Princeton University
Abstract: The efficient formation of carbon–carbon bonds remains one of the foremost aims of contemporary organic chemistry. Over the past century, the field has seen the rise of transition metal-mediated cross-coupling as a valuable strategy to forge these coveted bonds. Cross-coupling reactions have fundamentally reshaped retrosynthetic logic and established themselves as indispensable tools for the preparation of complex organic molecules. However, notable deficiencies remain for efficiently integrating C(sp3)-fragments in a modular manner, underscoring the urgent requirement for the development of adequate synthetic methods.This dissertation aims to further diversifying the synthetic chemist’s toolbox through metallaphotoredox catalysis, with a focus on enabling efficient formation of C(sp3)-enriched products. This was done through two main approaches: developing new organic methods enabling previously inaccessible disconnections and enhancing existing reactions recalcitrant to traditional generalization approaches. Chapter two introduces a deoxydifluoromethylation reaction, merging benzoxazolium-mediated alcohol activation and copper-mediated bond formation to replace aliphatic alcohols with their difluoromethyl bioisosteres, thereby facilitating the exploration of bioisostere chemical space. Chapter three expounds a novel approach towards the generalization of complex chemical reactions via additive mapping, increasing the utility of the metallaphotoredox decarboxylative arylation while revealing fundamental mechanistic insight into nickel-mediated cross-coupling processes. Chapter four focuses on the expansion of available C(sp2) coupling partners for C(sp2)–C(sp3) bond formation, successfully coupling aryl carboxylic acids with various underexplored C(sp3) coupling partners.
URI: http://arks.princeton.edu/ark:/88435/dsp012v23vx76s
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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