Palladium-catalyzed α-arylation of zinc enolates of esters: reaction conditions and substrate scope.
Palladium-catalyzed α-arylation of zinc enolates of esters: reaction conditions and substrate scope.
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DOI：
10.1021/jo401476f
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发表时间：
2013-09-06
期刊：
影响因子：
--
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Hama T;Ge S;Hartwig JF
报道了通过钯催化的芳基溴与酯的烯醇化锌的偶联来实现酯的分子间α-芳基化。已经开发了三种不同类型的烯醇化锌的反应。用分离的Reformatsky试剂，用由α-溴代酯和活化锌生成的Reformatsky试剂，以及用通过用氯化锌淬灭酯的烯醇化锂生成的烯醇化锌，以高产率发生酯的α-芳基化。使用烯醇化锌代替碱金属烯醇化物，极大地扩展了酯的芳基化的范围。反应在室温或70 °C下与含有氰基、硝基、酯、酮基、氟、可烯醇化氢、羟基或氨基官能团的溴芳烃和与溴吡啶发生。酯的范围包括无环乙酸酯、丙酸酯和异丁酸酯、α-烷氧基酯和内酯。用带有受阻五苯基二茂铁基二叔丁基膦（Q-phos）或高反应性二聚Pd（I）配合物{[P（t-Bu）3]PdBr}2的催化剂进行酯的烯醇化锌的芳基化。
The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2.
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