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New Strategies in Radical Chemistry and Their Application to the Construction of C(sp3)–C(sp3) Bonds in the Giese Reaction


Type

Thesis

Change log

Authors

Mistry, Sanesh 

Abstract

Considering inert and strong C(sp³)–C(sp³) bonds constitute the skeleton of all organic molecules, the development of novel methods for their construction remains of significant interest for the synthetic community. In this thesis, a unique platform to access C(sp³)-centred radicals, and their subsequent addition into electron deficient olefins to build saturated hydrocarbon frameworks (the Giese reaction), is investigated. The transformation merges two electrophilic components (an alkyl halide and an acceptor) in the presence of a silane and visible light irradiation.

Under these mild and extraordinarily simple conditions, visible light is anticipated to facilitate initiation derived from an interaction between the haloalkane and silane. The optimal setup was pleasingly compatible with a broad range of alkyl iodide and acceptor scaffolds, incorporating valuable functionalities such as free alcohols, protected amines and biologically active compounds. Further modifications of the reaction protocol provided the ability to generate C(sp³)-centred radicals from more synthetically tractable bromoalkane reagents, expanding the versatility and utility of this procedure.

Description

Date

2020-09-30

Advisors

Gaunt, Matt

Keywords

photochemistry, giese reaction

Qualification

Awarding Institution

University of Cambridge