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手性氨基锂芳基锌酸盐:简单高效的化学和对映选择性芳基转移试剂。

Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo- and Enantio-Selective Aryl Transfer Reagents.

作者信息

Chaumont-Olive Pauline, Rouen Mathieu, Barozzino-Consiglio Gabriella, Ben Abdeladhim Amel, Maddaluno Jacques, Harrison-Marchand Anne

机构信息

Normandie Univ, UNIROUEN, INSA de Rouen, CNRS, Laboratoire COBRA (UMR 6014 & FR 3038), 76000, Rouen, France.

出版信息

Angew Chem Int Ed Engl. 2019 Mar 4;58(10):3193-3197. doi: 10.1002/anie.201813510. Epub 2019 Jan 17.

Abstract

An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology.

摘要

使用手性三配位锂酰胺基芳基锌酸盐可促进对映选择性芳基转移,这些锌酸盐是易于获得的试剂,其手性基团可简单回收再利用。芳基化反应产率良好(二十种底物平均产率为60%),对映体过量值较高(平均对映体过量为95%ee)。无论底物带有邻位、间位或对位取代基,均会发生这种情况,并且对于醛官能团具有完全的化学选择性。腈、酯、酮和可烯醇化的底物等敏感基团能抵抗酸根试剂的作用,这保证了该方法具有广泛的适用范围。

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