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
{"title":"硼氢化钠还原2-卤代环己酮的溶剂效应","authors":"Daniela Rodrigues Silva,&nbsp;Lucas A. Zeoly,&nbsp;Pascal Vermeeren,&nbsp;Rodrigo A. Cormanich,&nbsp;Trevor A. Hamlin,&nbsp;Célia Fonseca Guerra,&nbsp;Matheus P. Freitas","doi":"10.1002/poc.4556","DOIUrl":null,"url":null,"abstract":"<p>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 NaBH<sub>4</sub>. 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 <i>cis</i> product observed experimentally.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2023-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Solvent effects on the sodium borohydride reduction of 2-halocyclohexanones\",\"authors\":\"Daniela Rodrigues Silva,&nbsp;Lucas A. Zeoly,&nbsp;Pascal Vermeeren,&nbsp;Rodrigo A. Cormanich,&nbsp;Trevor A. Hamlin,&nbsp;Célia Fonseca Guerra,&nbsp;Matheus P. Freitas\",\"doi\":\"10.1002/poc.4556\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>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 NaBH<sub>4</sub>. 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 <i>cis</i> product observed experimentally.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2023-06-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4556\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4556","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0

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。

摘要图片

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
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.
期刊最新文献
Issue Information Cover Image Cover Image Issue Information Enhanced Hyperpolarizabilities Through p‐Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide‐Based Zwitterions
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1