Nickel-catalyzed chemodivergent coupling of alcohols: efficient routes to access α,α-disubstituted ketones and α-substituted chalcones

TitleNickel-catalyzed chemodivergent coupling of alcohols: efficient routes to access α,α-disubstituted ketones and α-substituted chalcones
Publication TypeJournal Article
Year of Publication2024
AuthorsBansal, S, Punji, B
JournalChemistry- a european journal
Volume30
Issue15
Date PublishedMAR
Type of ArticleArticle
ISSN0947-6539
KeywordsAlcohols, dehydrogenative coupling, Metal-ligand cooperation, Nickel, substituted carbonyl compounds
Abstract

Chemodivergent (de)hydrogenative coupling of primary and secondary alcohols is achieved utilizing an inexpensive nickel catalyst, (6-OH-bpy)NiCl2. This protocol demonstrates the synthesis of branched carbonyl compounds, alpha,alpha-disubstituted ketones, and alpha-substituted chalcones via borrowing hydrogen strategy and acceptorless dehydrogenative coupling, respectively. A wide range of aryl-based secondary alcohols are coupled with various primary alcohols in this tandem dehydrogenation/hydrogenation reaction. The nickel catalyst, along with KOtBu or K2CO3, governed the selectivity for the formation of branched saturated ketones or chalcones. A preliminary mechanistic investigation confirms the reversible dehydrogenation of alcohols to carbonyls via metal-ligand cooperation (MLC) and the involvement of radical intermediates during the reaction. The chemodivergent nickel-catalyzed approach provides alpha,alpha-disubstituted ketones from aryl-substituted secondary alcohols and benzyl alcohols via the borrowing hydrogen (BH) strategy in the presence of KOtBu, whereas exclusively alpha-substituted chalcones were accomplished in the presence of mild base K2CO3 through an acceptorless dehydrogenative coupling (ADC) strategy. image

DOI10.1002/chem.202304082
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

4.3

Divison category: 
Organic Chemistry
Database: 
Web of Science (WoS)

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