Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

September 22, 2019

Title

Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

Author

Kikuchi Satoshi , Yoshida Shunsuke, Sugawara Yuudai , Yamada Wataru, Cheng Hau-Man, Fukui Kosuke, Sekine Kohei, Iwakura Izumi, Ikeno Taketo, Yamada Tohru

Year

2011

Journal

Bulletin of the Chemical Society of Japan 

Abstract

A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was found that the [3,3]-sigmatropic Meyer­Schuster-type rearrangement of the propargylic alcohol was mediated by CO2 in DMF to afford the corresponding ¡,¢-unsaturated carbonyl compounds in high yields. The silver salt combined with the chiral Schiff base ligand could be applied to enantioselective chemical CO2 incorporation into various bispropargylic alcohols to produce the corresponding cyclic carbonate in high yields with high enantioselectivity. The absolute configuration was determined by VCD spectroscopy as well as by X-ray analysis. These products were found to be active for the aminolysis reaction to afford the corresponding carbamate derivatives in high yields without any loss of optical purity.

Instrument

FVS-6000

Keywords

Vibrational circular dichroism, silver, carbon dioxide, propargylic derivative