Metal-free disproportionation of formic acid mediated by organoboranes. Issue 9 (3rd June 2016)

• Record Type: Journal Article
• Authors: Chauvier, Clément; Thuéry, Pierre; Cantat, Thibault
• Is Part Of: Chemical science. Volume 7:Issue 9(2016:Sep.)
• Page Start: 5680
• Page End: 5685
• Publication Date: 2016-06-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6sc01410k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : In the presence of dialkylboranes, formic acid is converted to formaldehyde and methanol derivatives. This is the first example of formate disproportionation under metal-free conditions. Mechanistic studies highlight the role of transient borohydrides in the reduction of formates and this is further shown in transfer hydroboration for aldehyde reduction. Abstract : In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first example of the disproportionation of formate anions under metal-free conditions. Capitalizing on both experimental and computational (DFT) mechanistic considerations, the role of transient borohydride is highlighted in the reduction of formates and this reactivity was further exemplified in the methylation of TMP (2, 2, 6, 6-tetramethylpiperidine) and in the transfer hydroboration reactions for the reduction of aldehydes.