通过串联NHC催化的动态动力学拆分和室温脱羧反应实现功能化环戊烯：机理洞察与合成应用
Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: mechanistic insight and synthetic application.
作者信息
Cohen Daniel T, Johnston Ryne C, Rosson Nicholas T, Cheong Paul Ha-Yeon, Scheidt Karl A
机构信息
Department of Chemistry, Center for Molecular Innovation and Drug Discovery, Chemistry of Life Processes Institute, Northwestern University, Silverman Hall, Evanston, Illinois 60208, USA.
出版信息
Chem Commun (Camb). 2015 Feb 14;51(13):2690-3. doi: 10.1039/c4cc09308a.
Abstract
An unusual room temperature β-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor β-agonist. A computational study probed the underlying factors facilitating unprecedented, rapid decarboxylation. Aryl substitution promotes faster reaction in the retro-[2+2] as a result of conjugative stabilization with the forming olefin. Additionally, the configuration of the α-ester in these fused β-lactones leads to differential decarboxylation rates.
摘要
一种不寻常的室温β-内酯脱羧反应促进了雌激素受体β激动剂环戊烷核心的五步对映选择性形式合成。一项计算研究探究了促进前所未有的快速脱羧反应的潜在因素。芳基取代由于与形成的烯烃的共轭稳定作用，促进了逆-[2+2]反应中更快的反应。此外，这些稠合β-内酯中α-酯的构型导致不同的脱羧速率。
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