Additions of Organomagnesium Halides to alpha-Alkoxy Ketones: Revision of the Chelation-Control Model

作者:Read Jacquelyne A; Yang Yingying; Woerpel K A
来源:Organic Letters, 2017, 19(13): 3346-3349.
DOI:10.1021/acs.orglett.7b01161

摘要

The chelation-control model explains the high diastei'eoselectivity Obtained in additions of organoinetallic nucleophiles to alpha-alkoxy ketones but fails for reactions of allylmagnesiuin halides. Low diastereoselectivity in ethereal Solvents results from no chelation-induced rate acceleration. Additions of allylmagnesium bromide to carbonyl compounds are diastereoselective using CH2Cl2 as the solvent even though rate acceleration is still absent. Stereoselectivity likely arises from the predominance of the chelated form in solution. Therefore, a revised chelation-control model is proposed.

  • 出版日期2017-7-7