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在 (V) 中进行第二代催化酶选择性核性脱对称:提高了通用性,效率和模块性

Michele Formica¹, Branislav Ferko¹, Thomas Marsh¹

¹Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.

Angewandte Chemie (International ed. in English)

|February 21, 2024

概括

这项研究引入了一种改进的催化方法,用于以enantioselective方式合成 (V) 化合物. 这种新方法扩大了基质的范围,并提高了创建多种有机分子的效率.

科学领域:

有机化学化学有机化学
不对称的催化剂.
合成有机化学合成有机化学

背景情况:

类固醇 (V) 化合物是各种化学应用中的关键构件.
现有的酶选择性合成方法往往在范围和效率上有局限性.
开发实用和多功能催化系统仍然是一个关键的挑战.

研究的目的:

介绍第二代催化双相策略,用于化合物的选择性合成.
通过提高催化效率和基质范围来扩大可访问的有机化合物的范围.
为了研究选择性和立体化学结果的机制基础.

主要方法:

使用双功能的伊米诺酸 (BIMP) 催化剂进行核性脱对称的前体P(V) 前体.
采用一种新的尿素BIMP催化剂和 thiaziolidinone 脱离组,以提高性能.
执行随后的等离子特异替代反应和密度函数理论 (DFT) 计算.

主要成果:

从有限的丰富中间体中获得C,N,O和S替代P (V) 化合物的分离合成.
与以前的方法相比,证明了显著更广泛的基质范围,更高的反应效率和更好的实用性.
DFT计算阐明了S_N2@P反应中的酶选择性和立体化学途径的起源.

结论:

开发的第二代催化系统提供了一个大大改进的和实用的方法,用于enantioselective (V) 合成.
新的催化剂/离开组组合增强了普遍性和效率,使人们能够访问各种有机结构.
了解机械细节为进一步的催化剂设计和反应优化提供了洞察力.

关键词:

这是一个双功能的双功能.脱对称化的脱对称化具有抗选择性的人类选择性.亚米诺酸的含量是多少是一种的物质.

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