Evidence of Cu I /Cu II Redox Process by X‐ray Absorption and EPR Spectroscopy: Direct Synthesis of Dihydrofurans from β‐Ketocarbonyl Derivatives and Olefins

Yi, Hong; Liao, Zhixiong; Zhang, Guanghui; Zhang, Guoting; Fan, Chao; Zhang, Xu; Bunel, Emilio E.; Pao, Chih‐Wen; Lee, Jyh‐Fu; Lei, Aiwen

doi:10.1002/chem.201503822

Evidence of Cu ^I /Cu ^II Redox Process by X‐ray Absorption and EPR Spectroscopy: Direct Synthesis of Dihydrofurans from β‐Ketocarbonyl Derivatives and Olefins

Journal Article · Tue Nov 10 23:00:00 EST 2015 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201503822· OSTI ID:1786152

Yi, Hong; Liao, Zhixiong; Zhang, Guanghui; Zhang, Guoting; Fan, Chao; Zhang, Xu; Bunel, Emilio E.; Pao, Chih‐Wen; Lee, Jyh‐Fu; Lei, Aiwen

Abstract

The Cu ^I /Cu ^II and Cu ^I /Cu ^III catalytic cycles have been subject to intense debate in the field of copper‐catalyzed oxidative coupling reactions. A mechanistic study on the Cu ^I /Cu ^II redox process, by X‐ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopies, has elucidated the reduction mechanism of Cu ^II to Cu ^I by 1,3‐diketone and detailed investigation revealed that the halide ion is important for the reduction process. The oxidative nature of the thereby‐formed Cu ^I has also been studied by XAS and EPR spectroscopy. This mechanistic information is applicable to the copper‐catalyzed oxidative cyclization of β‐ketocarbonyl derivatives to dihydrofurans. This protocol provides an ideal route to highly substituted dihydrofuran rings from easily available 1,3‐dicarbonyls and olefins.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC02-06CH11357

OSTI ID:: 1786152

Alternate ID(s):: OSTI ID: 1241302

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 52 Vol. 21; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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