The Direct Conversion of Esters to Ketones Enabled by a Traceless Activating Group.

Autor: Fier PS; Department of Process Research and Development, Merck & Co., Inc., Rahway, New Jersey 07065, United States., Roberts RA; Department of Process Research and Development, Merck & Co., Inc., Rahway, New Jersey 07065, United States., Larson RT; Department of Process Research and Development, Merck & Co., Inc., Rahway, New Jersey 07065, United States.
Jazyk: angličtina
Zdroj: Organic letters [Org Lett] 2023 May 05; Vol. 25 (17), pp. 3131-3135. Date of Electronic Publication: 2023 Apr 26.
DOI: 10.1021/acs.orglett.3c00992
Abstrakt: We report here the design and development of a method for the single-step conversion of esters to ketones with simple reagents. The selective transformation of esters to ketones, rather than tertiary alcohols, is made possible by the use of a transient sulfinate group on the nucleophile that activates the adjacent carbon toward deprotonation to form a carbanion that adds to the ester, followed by a second deprotonation to prevent further addition. The resulting dianion undergoes spontaneous fragmentation of the SO 2 group upon quenching with water to reveal the ketone product.
Databáze: MEDLINE
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