Electroreductive formylation of activated alcohols radical-polar crossover

• Published in: Chemical communications (Cambridge, England) England), 2023-05, Vol.59 (38), p.5733-5736
• Main Authors: Kang, Jungtaek, Cho, Heyjin, Kim, Hyunwoo
• Format: Article
• ISSN: 1359-7345; 1364-548X
• DOI: 10.1039/d3cc01529g

The direct synthesis of sterically hindered aldehydes is highly challenging. Herein, we report a direct approach to generate such compounds via electroreductive cleavage of the C(sp 3 )-O bond of activated alcohols. Under the established reaction conditions, benzylic radical intermediates were efficiently generated. A subsequent radical-polar crossover generated carbanions that further reacted with N , N -dimethylformamide to form various aldehydes with tertiary or quaternary benzylic carbon centers. The feasibility of a gram-scale synthesis was also demonstrated. This reaction is also operated in a simple undivided cell, which avoids the use of any transition metal catalysts, toxic gas, and reductants. The direct synthesis of sterically hindered aldehydes involves the electroreductive cleavage of the C-O bond in activated alcohols, generating carbanions that can then react with N , N -dimethylformamide.