Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles

被引:16
作者
Trost, Barry M. [2 ]
Jiao, Zhiwei [1 ]
Gholami, Hadi [2 ]
机构
[1] Sun Yat Sen Univ, Sch Chem, Guangzhou 510275, Peoples R China
[2] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
关键词
ALPHA-CYANO ESTERS; BETA-KETO-ESTERS; DECARBOXYLATIVE ALLYLATION; ENANTIOSELECTIVE SYNTHESIS; SYNTHETIC APPLICATIONS; MALONATE ESTERS; QUATERNARY; SUBSTITUTION; DEALKOXYCARBONYLATIONS; CYCLOADDITION;
D O I
10.1039/d1sc02599f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An efficient palladium-catalyzed AAA reaction with a simple alpha-sulfonyl carbon anion as nucleophiles is presented for the first time. Allyl fluorides are used as superior precursors for the generation of pi-allyl complexes that upon ionization liberate fluoride anions for activation of silylated nucleophiles. With the unique bidentate diamidophosphite ligand ligated palladium as catalyst, the in situ generated alpha-sulfonyl carbon anion was quickly captured by the allylic intermediates, affording a series of chiral homo-allylic sulfones with high efficiency and selectivity. This work provides a mild in situ desilylation strategy to reveal nucleophilic carbon centers that could be used to overcome the pK(a) limitation of "hard" nucleophiles in enantioselective transformations.
引用
收藏
页码:10532 / 10537
页数:6
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