硼氢化钠还原2-卤代环己酮的溶剂效应

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2023-06-23 DOI:10.1002/poc.4556
Daniela Rodrigues Silva, Lucas A. Zeoly, Pascal Vermeeren, Rodrigo A. Cormanich, Trevor A. Hamlin, Célia Fonseca Guerra, Matheus P. Freitas
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摘要

采用竞争性实验和密度泛函理论计算相结合的方法研究了硼氢化钠还原2-X-环己酮(X=H, Cl, Br)的立体选择性和反应活性。我们的研究结果表明,氢化物的加成是通过一个晚期的过渡态进行的,在这个过渡态中,C-H键几乎形成,这与NaBH4的温和还原能力一致。从2-卤代环己酮到未取代环己酮的反应势垒减小,与竞争性实验中观察到的相对反应性一致。此外,我们提供了一个方案,以解决长期存在的问题,正确模拟氢化物添加到邻极性取代的羰基的轴-赤道面选择性。隐式溶剂化与显式溶剂分子的结合对于再现实验中观察到的顺式产物的立体选择性形成至关重要。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Solvent effects on the sodium borohydride reduction of 2-halocyclohexanones

We have investigated the stereoselectivity and reactivity of the sodium borohydride reduction of 2-X-cyclohexanones (X=H, Cl, Br) using a combined approach of competitive experiments and density functional theory calculations. Our results show that the hydride addition proceeds via a late transition state in which the C–H bond is nearly formed, consistent with the mild reducing power of NaBH4. The reaction barrier decreases from the 2-halocyclohexanones to the unsubstituted cyclohexanone, in line with relative reactivities observed in the competitive experiments. Furthermore, we provide a protocol to solve the longstanding issue of properly modelling the axial–equatorial facial selectivity of hydride addition to the carbonyl group substituted with a vicinal polar group. The inclusion of implicit solvation in combination with an explicit solvent molecule is crucial to reproduce the stereoselective formation of the cis product observed experimentally.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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