α-烯基-β-二酮的逆合成分析：由乙炔、酮和酰氯经区域和立体选择性两步法合成高度芳基化的衍生物

Retrosynthetic Analysis of α-Alkenyl-β-Diketones: Regio- and Stereoselective Two-Step Synthesis of Highly Arylated Representatives from Acetylenes, Ketones, and Acyl Chlorides.

作者信息

Shabalin Dmitrii A, Ivanova Elena V, Ushakov Igor' A, Schmidt Elena Yu, Trofimov Boris A

机构信息

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation.

出版信息

J Org Chem. 2020 Jul 2;85(13):8429-8436. doi: 10.1021/acs.joc.0c00768. Epub 2020 Jun 22.

DOI:10.1021/acs.joc.0c00768

PMID:32490679

Abstract

Highly arylated α-alkenyl-β-diketones are synthesized a two-step sequence consisting of () potassium -butoxide/DMSO-catalyzed ()-stereoselective C-H functionalization of ketones with acetylenes followed by () magnesium bromide etherate/DIPEA-soft enolization of the formed β,γ-unsaturated ketones and regioselective acylation with acyl chlorides. The method is compatible with a broad range of substrates and shown to be applicable as an intermediate stage in the construction of polyarylated heterocycles.

摘要

高度芳基化的α-烯基-β-二酮通过两步反应序列合成，该序列包括：（i）叔丁醇钾/二甲基亚砜催化的酮与乙炔的（Z）-立体选择性C-H官能化反应，随后（ii）溴化镁乙醚/二异丙基乙胺对生成的β，γ-不饱和酮进行温和烯醇化反应以及与酰氯的区域选择性酰化反应。该方法与多种底物兼容，并被证明可作为构建多芳基化杂环的中间阶段。