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Applications of γ,δ-Unsaturated Ketones Synthesized by Copper-Catalyzed Cascade Addition of Vinyl Grignard Reagents to Esters
Accounts of Chemical Research ( IF 18.3 ) Pub Date : 2018-10-05 00:00:00 , DOI: 10.1021/acs.accounts.8b00388
Antoine Douchez 1 , Azade Geranurimi 1 , William D. Lubell 1
Affiliation  

γ,δ-Unsaturated ketones, so-called homoallylic ketones, have served as versatile building blocks for the synthesis of a variety of heterocycles, carbocycles, natural products, and reactive intermediates. Procured by a variety of processes, including conjugate addition of vinyl organometallic reagents to unsaturated ketones, allylation of silyl enol ethers, and rearrangements, homoallylic ketones are often synthesized by step-intensive methods. The cascade addition of 2 equiv of vinyl Grignard reagent to a carboxylate was reported by the Lubell laboratory in 2003 to give effective access to homoallylic ketones from a variety of aromatic, aliphatic, and α-amino methyl esters. Employing readily accessible vinyl magnesium halides in the presence of a catalytic amount of copper salt, this cascade reaction provides high yields of homoallylic ketones with minimal side product by a process featuring the assembly and collapse of a tetrahedral intermediate with expulsion of alkoxide ion, followed by conjugate addition to the resulting enone.

中文翻译:

铜格纳德试剂的铜催化级联加成合成的γ,δ-不饱和酮在酯中的应用

γ,δ-不饱和酮,即所谓的均烯丙基酮,已成为合成各种杂环,碳环化合物,天然产物和反应性中间体的通用结构单元。通过多种方法获得,包括将乙烯基有机金属试剂共轭加成至不饱和酮,甲硅烷基烯醇醚的烯丙基化和重排,均烯丙基酮通常通过分步密集的方法合成。Lubell实验室在2003年报告称,将2当量的乙烯基格氏试剂级联添加到羧酸酯中可以有效地从各种芳香族,脂肪族和α-氨基甲基酯中获得均质酮。在催化量的铜盐存在下,使用容易获得的乙烯基卤化镁,
更新日期:2018-10-05
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