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Title: Iron-mediated C-H coupling of arylsulfides and simple terminal alkenes
Author: Cavanagh, Craig
ISNI:       0000 0004 6495 8795
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2016
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The use of directing groups in C-H functionalisation reactions provides a means to control the regioselectivity of such processes. Previous work in the Procter group reported the sulfoxide-directed metal-free C-H alkylation of arenes with organosilane nucleophiles. Attempts to expand this work by carrying out a similar process directly from the sulfide oxidation level, utilising an Fe(III) oxidant, a diarylsulfide and an alkene are discussed herein. During these investigations, it was discovered that the use of simple, unfunctionalised olefins selectively gave linear products of formal chloroarylation, which represents a novel transformation. Following optimisation studies, the reaction proceeded in good to moderate yield under exceptionally mild conditions with a range of alkene and sulfide coupling partners, although sulfides do require a particular oxygenation pattern in the aryl ring undergoing coupling. Based on various experimental observations, a single electron oxidation process is believed to be responsible for the desired reactivity. A number of manipulations of the chlorinated products are demonstrated, including their use in an expedient synthesis of important dihydrobenzofuran motifs. The original sulfur directing-group has also been used as a handle for further elaboration of these interesting structures.
Supervisor: Procter, David Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available