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Bifunctional Silver(I) Complex‐Catalyzed CO 2 Conversion at Ambient Conditions: Synthesis of α‐Methylene Cyclic Carbonates and Derivatives
Author(s) -
Song QingWen,
Chen WeiQiang,
Ma Ran,
Yu Ao,
Li QiuYue,
Chang Yao,
He LiangNian
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201402921
Subject(s) - chemistry , bifunctional , catalysis , nucleophile , triphenylphosphine , methylene , alcohol , nucleophilic substitution , intramolecular force , organic chemistry , medicinal chemistry , photochemistry
The chemical conversion of CO 2 at atmospheric pressure and room temperature remains a great challenge. The triphenylphosphine complex of silver(I) carbonate was proved to be a robust bifunctional catalyst for the carboxylative cyclization of propargylic alcohols and CO 2 at ambient conditions leading to the formation of α‐methylene cyclic carbonates in excellent yields. The unprecedented performance of [(PPh 3 ) 2 Ag] 2 CO 3 is presumably attributed to the simultaneous activation of CO 2 and propargylic alcohol. Moreover, the highly compatible basicity of the catalytic species allows propargylic alcohol to react with CO 2 leading to key silver alkylcarbonate intermediates: the bulkier [(Ph 3 P) 2 Ag I ] + effectively activates the carbon–carbon triple bond and enhances O‐nucleophilicity of the alkylcarbonic anion, thereby greatly promoting the intramolecular nucleophilic cyclization. Notably, this catalytic protocol also worked well for the reaction of propargylic alcohols, secondary amines, and CO 2 (at atmospheric pressure) to afford β‐oxopropylcarbamates.