Exploring regioselectivity in 1,3-dipolar cycloaddition of thioamides, selenoamides, and amides with propadienyl cation derivatives using density functional theory
{"title":"Exploring regioselectivity in 1,3-dipolar cycloaddition of thioamides, selenoamides, and amides with propadienyl cation derivatives using density functional theory","authors":"Vanishree Shankar Naik, Ganga Periyasamy","doi":"10.1002/poc.4646","DOIUrl":null,"url":null,"abstract":"<p>This study explores the potential mechanisms (Paths 1 and 2) involved in the regioselective dipolar cycloaddition of thioamides, selenoamides, and amides with propargyl alcohol using density functional theory (DFT). Our calculations reveal that the initial step involves the formation of a cation with catalyst. Subsequently, isomerization occurs between cations I and II via 1,3-hydride transfer in the second step. We analyzed the global reactivity index and frontier molecular orbital (FMO) theory to gain insights into the mechanism. In the third step, chalcoamides attack cations I and II, forming an intermediate. The formation of a five-member ring intermediate constitutes the fourth step, followed by hydrogen transfer to produce stable five-member heterazole compounds in the final step. We demonstrated the influence of substituents in the electrophile by employing various electron-withdrawing and donating groups. Additionally, we examined the effect of the dielectric medium on the reaction barrier using polarizable continuum model. Thus, this study provides valuable insights for the rational design of more efficient 1,3-dipolar cycloaddition reactions yielding regioselective products.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 10","pages":""},"PeriodicalIF":1.9000,"publicationDate":"2024-07-04","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.4646","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
Abstract
This study explores the potential mechanisms (Paths 1 and 2) involved in the regioselective dipolar cycloaddition of thioamides, selenoamides, and amides with propargyl alcohol using density functional theory (DFT). Our calculations reveal that the initial step involves the formation of a cation with catalyst. Subsequently, isomerization occurs between cations I and II via 1,3-hydride transfer in the second step. We analyzed the global reactivity index and frontier molecular orbital (FMO) theory to gain insights into the mechanism. In the third step, chalcoamides attack cations I and II, forming an intermediate. The formation of a five-member ring intermediate constitutes the fourth step, followed by hydrogen transfer to produce stable five-member heterazole compounds in the final step. We demonstrated the influence of substituents in the electrophile by employing various electron-withdrawing and donating groups. Additionally, we examined the effect of the dielectric medium on the reaction barrier using polarizable continuum model. Thus, this study provides valuable insights for the rational design of more efficient 1,3-dipolar cycloaddition reactions yielding regioselective products.
本研究利用密度泛函理论(DFT)探讨了硫代酰胺、硒酰胺和酰胺与丙炔醇进行区域选择性双极环加成的潜在机理(路径 1 和 2)。我们的计算显示,第一步涉及阳离子与催化剂的形成。随后,在第二步中,阳离子 I 和 II 之间通过 1,3- 氢转移发生异构化。我们分析了全局反应性指数和前沿分子轨道(FMO)理论,以深入了解其机理。在第三步中,恰尔酰胺攻击阳离子 I 和 II,形成中间体。第四步形成五元环中间体,最后一步通过氢转移生成稳定的五元杂唑化合物。我们通过使用各种吸电子和供电子基团,证明了亲电子体中取代基的影响。此外,我们还利用可极化连续体模型研究了介电介质对反应屏障的影响。因此,这项研究为合理设计更高效的 1,3-二极环加成反应提供了宝贵的见解,从而产生具有区域选择性的产物。
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.