Domino Ring Expansion: Regioselective Access to 9‐Membered Lactones with a Fused Indole Unit from 2‐Nitrophenyl‐1, 3‐cyclohexanediones. Issue 9 (16th January 2018)

• Record Type: Journal Article
• Authors: Loya, David Reyes; Jean, Alexandre; Cormier, Morgan; Fressigné, Catherine; Nejrotti, Stefano; Blanchet, Jérôme; Maddaluno, Jacques; De Paolis, Michaël
• Is Part Of: Chemistry. Volume 24:Issue 9(2018)
• Page Start: 2080
• Page End: 2084
• Publication Date: 2018-01-16
• Subjects: domino reactions -- lactones -- regioselectivity -- ring expansions; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201705645
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The domino anionic fragmentation of 2‐nitrophenyl‐1, 3‐cyclohexanediones containing an electrophilic appendage such as aldehyde and epoxide is disclosed. This reaction, initiated by a series of nucleophiles, involves the generation of an intermediate hydroxylate followed by the regioselective formation and fragmentation of an intermediate lactolate into enolate. This strategy, devoid of any protecting group, enlarges the initial ring and provides an original access to decorated 9‐membered lactones with a fused indole unit. Abstract : The domino ring expansion of 2‐nitrophenyl‐1, 3‐cyclohexanediones connected to an electrophilic appendage–aldehyde and epoxide–into 9‐membered lactones was developed. Regio‐ and stereoselectivity were observed upon treatment with carbon, aza, bromide, and hydride nucleophiles, giving access to highly substituted lactones.