Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation

A catalytic method for the direct electrophilic cyanation of C(sp²)–H nucleophiles with sodium cyanate (NaOCN) is reported. Mechanistic experiments show that under solid-liquid phase transfer, an inorganic cyanate is activated by halide displacement on a halophosphonium. Redox catalysis is enabled by the usage of a strained phosphine (phosphetane) so that catalyst turnover from phosphine oxide to phosphine can be easily achieved by the usage of a terminal hydrosilane reductant. These results demonstrate the feasibility of deoxyfunctionalization of insoluble inorganic salts by Pᴵᴵᴵ/Pⱽ=O catalyzed phase transfer activation, as exemplified by C(sp²)–H cyanation with NaOCN as the “CN⁺” source.

Name thesis:degree_name

Bachelor

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2024

Author dc:creator

• Hu, Shicheng

Advisor dc:contributor.advisor

• Radosevich, Alexander T.

Statement dc:rights

• In Copyright - Educational Use Permitted
• Copyright retained by author(s)

Licence dc:rights.uri

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

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/157726

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/157726