Electricity Driven 1,3‐Oxohydroxylation of Donor‐Acceptor Cyclopropanes: a Mild and Straightforward Access to β‐Hydroxy Ketones

• Published in: European journal of organic chemistry Vol. 2021; no. 36; pp. 5053 - 5057
• Main Authors: Saha, Debarshi, Maajid Taily, Irshad, Banerjee, Prabal
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 24.09.2021; Wiley Subscription Services, Inc
• Subjects: 1,3-Oxohydroxylation; Aryl activation; Chemistry; Chemistry, Organic; Cyclopropane; Electron clouds; Electroorganic synthesis; Endoperoxide intermediate; Ketones; Organic compounds; Oxidizing agents; Oxygen; Physical Sciences; Science & Technology; β-Hydroxy ketones; OXIDATION; Electroorganic synthesis; 1; ACID; BIOSYNTHESIS; beta-Hydroxy ketones; RING-OPENING REACTIONS; Aryl activation; REACTIVITY; 3-Oxohydroxylation; DERIVATIVES; Endoperoxide intermediate
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202101022

An unprecedented external oxidant‐free electrochemical protocol for 1, 3‐oxohydroxylation of donor‐acceptor cyclopropane is disclosed. The strategy encompasses the activation of the labile π‐electron cloud of the aryl ring to cleave the strained Csp3−Csp3 bond of cyclopropane to afford the β‐hydroxy ketones via insertion of molecular oxygen. More significantly, based on the detailed mechanistic investigations and cyclic voltammetry experiments, a plausible mechanism is proposed. A facile protocol entailing the principle of electrochemical oxidation of aryl rings has been utilized to relieve the strain of donor‐acceptor cyclopropane and further trap the molecular oxygen to deliver the 1,3‐bifunctionalized product. Hence, the methodology bestows a novel route towards the scalable synthesis of β‐hydroxy ketones.