MeZnOMe‐mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway

• Published in: Applied organometallic chemistry Vol. 32; no. 9
• Main Authors: Fu, Ying, Ma, Xian‐Zhen, Shi, Chun‐Zhao, Shen, Tong, Du, Zhengyin
• Format: Journal Article
• Language: English
• Published: HOBOKEN Wiley 01.09.2018; Wiley Subscription Services, Inc
• Subjects: aldehyde; Aldehydes; Aromatic compounds; Chemistry; Chemistry, Applied; Chemistry, Inorganic & Nuclear; Functional groups; Grignard reagent; ketone; Ketones; Lithium chloride; Oppenauer oxidation; Oxidation; Physical Sciences; Reagents; Science & Technology; Substrates; transmetalation; Oppenauer oxidation; aldehyde; TERMINAL ALKYNES; MAGNESIUM 2-ETHOXYETHOXIDE; AROMATIC-ALDEHYDES; ADDITION-OPPENAUER OXIDATION; TISHCHENKO REACTION; ketone; ORGANOZINC REAGENTS; ALCOHOLS; Grignard reagent; CANNIZZARO; ARYL KETONES; TETRAHYDROFURAN; transmetalation
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.4462

A novel organozincate of RMgX ⋅MeZnOMe ⋅LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ⋅LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance. A novel organozincate of RMgX·MeZnOMe·LiCl type, in situ generated via transmetalation of Grignard reagent RMgBr·LiCl with MeZnOMe, was shown to be an excellent organometallic species in the nucleophilic addition‐Oppenauer oxidation of aldehyde (NAOOA) to produce aromatic ketones in high yield.