Novel metal- and main group-catalyzed methods for modulating molecular oxygenation

Synthetic methodologies frequently rely on oxygen functionality as a synthetic handle to enable structural modification of organic molecules; therefore, methods that enable new ways to modulate oxygen content in molecular structure facilitate structural diversification. This thesis details the development of catalytic methods affecting oxygen incorporation in organic molecules. These methods make use of fundamentally distinct strategies in bond activation to oxygenate and deoxygenate molecular architectures. First, a metal induced bond-weakening, dual-catalytic strategy was implemented to oxidize the benzylic positions of azaheterocycles. Coordination of a metal catalyst to the nitrogen lone pair is thought to induce weakening of proximal C-H bonds such that a radical catalyst with tunable chemoselectivity breaks this weakened bond. In the presence of an oxygen atmosphere, this leads to carbon-oxygen bond formation.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2019

Author dc:creator

• Cooper, Julian C.(Julian Colton)

Advisor dc:contributor.advisor

• Alexander T. Radosevich.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/124046

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/124046