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

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.

Level dc:type.qualificationlevel

Doctoral

Grantor dc:publisher.institution

University of Cambridge

Year dc:date.issued

2020

Author dc:creator

• Mistry, Sanesh

Advisor dc:contributor.advisor

• Gaunt, Matt

• photochemistry
• giese reaction

Licence

• https://www.repository.cam.ac.uk/bitstreams/393ee932-edb0-4229-809f-83c918540cd0/download
• https://www.rioxx.net/licenses/all-rights-reserved/

Language dc:language

eng

DOI dc:identifier.doi

https://doi.org/10.17863/CAM.68792

OAI identifier oai:identifier

oai:www.repository.cam.ac.uk:1810/321673