Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles

A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity.

Name thesis:degree_name

Master

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2022

Author dc:creator

• Pombar, Gisselle

Advisor dc:contributor.advisor

• Radosevich, Alexander T.

Statement dc:rights

• In Copyright - Educational Use Permitted
• Copyright MIT

Licence dc:rights.uri

• http://rightsstatements.org/page/InC-EDU/1.0/

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/147263

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/147263