Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation
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hu-shicheng-thesis_corrected_1022.pdf
Description
Thesis PDF
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2.88 MB
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Adobe PDF
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fc2ee21bbd4dcdcb7175952b3a086453
Author(s)
Hu, Shicheng
Advisor(s)
Radosevich, Alexander T.
Date Issued
May 2024
Publisher
Massachusetts Institute of Technology
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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