Silver(I)-Catalyzed Synthesis of β-Oxopropylcarbamates from Propargylic Alcohols and CO2 Surrogate: A Gas-Free Process

• Published in: ChemSusChem Vol. 8; no. 23; pp. 3967 - 3972
• Main Authors: Song, Qing-Wen, Zhou, Zhi-Hua, Yin, Hong, He, Liang-Nian
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 07.12.2015
• Subjects: Alkynes - chemistry; Carbamates - chemical synthesis; Carbamates - chemistry; Carbon Dioxide - chemistry; Catalysis; Chemistry Techniques, Synthetic; homogeneous catalysis; nitrogen heterocycles; Propanols - chemistry; silver; Silver - chemistry; synthetic methods; silver; carbon dioxide chemistry; homogeneous catalysis; synthetic methods; nitrogen heterocycles
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201501176

The utilization of carbon dioxide poses major challenges owing to its high thermodynamic stability and kinetic inertness. To circumvent these problems, a simple reaction system is reported comprising ammonium carbamates as carbon dioxide surrogates, propargylic alcohols, and a silver(I) catalyst, for the effective conversion of a wide range of alcohols and secondary amines into the corresponding β‐oxopropylcarbamates. A key feature of this strategy includes quantitative use of a carbon resource with high product yields under gas‐free and mild reaction conditions. Notably, this catalytic protocol also works well for the carboxylative cyclization of propargylic amines and carbon dioxide surrogates to afford 2‐oxazolidinones. Workaround: The reactivity of CO2 can be improved by using a silver(I) catalyst for effective conversion into propargylic alcohol‐based surrogates, which react to β‐oxopropylcarbamates under gas‐free and mild reaction conditions. This opens up an alternative way to prepare value‐added products with stoichiometric amounts of CO2.