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()-α,β-不饱和酯的立体选择性合成:三乙胺催化的烯醇磷酸酯的烯丙基重排

Stereoselective synthesis of ()-α,β-unsaturated esters: triethylamine-catalyzed allylic rearrangement of enol phosphates.

作者信息

Zhang Yulong, Guo Huichuang, Wu Qian, Bi Xiaojing, Shi Enxue, Xiao Junhua

机构信息

State Key Laboratory of NBC Protection for Civilian Beijing 102205 P. R. China

出版信息

RSC Adv. 2023 May 11;13(20):13511-13515. doi: 10.1039/d3ra02430j. eCollection 2023 May 2.

Abstract

α,β-Unsaturated esters are key structural motifs widely distributed in various biologically active molecules, and their /-stereoselective synthesis has always been considered highly attractive in organic synthesis. Herein, we present a >99% ()-stereoselective one-pot synthetic approach towards β-phosphoroxylated α,β-unsaturated esters a mild trimethylamine-catalyzed 1,3-hydrogen migration of the corresponding unconjugated intermediates derived from the solvent-free Perkow reaction between low-cost 4-chloroacetoacetates and phosphites. Versatile β,β-disubstituted ()-α,β-unsaturated esters were thus afforded with full ()-stereoretentivity by cleavage of the phosphoenol linkage Negishi cross-coupling. Moreover, a stereoretentive ()-rich mixture of a α,β-unsaturated ester derived from 2-chloroacetoacetate was obtained and both isomers were easily afforded in one operation.

摘要

α,β-不饱和酯是广泛分布于各种生物活性分子中的关键结构基序,其立体选择性合成在有机合成中一直备受关注。在此,我们报道了一种对β-磷酰氧基化α,β-不饱和酯具有>99%立体选择性的一锅法合成方法——一种温和的三甲胺催化的1,3-氢迁移反应,该反应涉及由低成本的4-氯乙酰乙酸酯与亚磷酸酯在无溶剂Perkow反应中衍生出的相应非共轭中间体。通过磷烯醇键的裂解——根岸交叉偶联反应,从而以完全的立体保持性得到了通用的β,β-二取代()-α,β-不饱和酯。此外,还获得了一种由2-氯乙酰乙酸酯衍生的α,β-不饱和酯的富含()-异构体的立体保持混合物,并且两种异构体可在一次操作中轻松获得。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/da52/10173029/624c63bfc62b/d3ra02430j-f1.jpg

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