Related Experiment Video
Updated: Aug 16, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Oxidation-Triggered Single-Carbon Atom Doping into Acyl Chlorides Using N-Isocyanide
Hayato Fujimoto1,2, Reona Ikeda1, Mamoru Tobisu1,2
1Department of Applied Chemistry, Graduate School of Engineering, The University of Osaka, Suita, Osaka565-0871, Japan.
Abstract:
Atomic carbon is an attractive intermediate because it can form four new covalent bonds in a single transformation, but its synthetic use is limited by its short lifetime. Herein, we report an oxidation-triggered carbon-atom insertion into acyl chlorides using bench-stable N-isocyaniminophosphorane (PINC). Unlike our previous thermal/Rh-catalyzed protocol, this method proceeds at room temperature to afford cyclic α-chloro ketones. Mechanistic studies support oxidation-induced diazo formation from a phosphazine intermediate, followed by carbene generation.
Related Concept Videos
Preparation of Nitriles
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H] allows...
Preparation of Carboxylic Acids: Hydrolysis of Nitriles

