Bifunctional Silver(I) Complex‐Catalyzed CO2 Conversion at Ambient Conditions: Synthesis of α‐Methylene Cyclic Carbonates and Derivatives. Issue 5 (15th December 2014)

• Record Type: Journal Article
• Authors: Song, Qing‐Wen; Chen, Wei‐Qiang; Ma, Ran; Yu, Ao; Li, Qiu‐Yue; Chang, Yao; He, Liang‐Nian
• Is Part Of: ChemSusChem. Volume 8:Issue 5(2015:Mar.)
• Page Start: 821
• Page End: 827
• Publication Date: 2014-12-15
• Subjects: Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201402921
• Languages: English
• ISSNs: 1864-5631

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The chemical conversion of CO₂ 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 CO₂ at ambient conditions leading to the formation of α‐methylene cyclic carbonates in excellent yields. The unprecedented performance of [(PPh₃)₂Ag]₂CO₃ is presumably attributed to the simultaneous activation of CO₂ and propargylic alcohol. Moreover, the highly compatible basicity of the catalytic species allows propargylic alcohol to react with CO₂ leading to key silver alkylcarbonate intermediates: the bulkier [(Ph₃P)₂Ag^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 CO₂ (at atmospheric pressure) to afford β‐oxopropylcarbamates.</p> </abstract>