双硼杂环烯：Diels-Alder 反应的计算研究

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-10-22 DOI:10.1039/d4cp03615h

Changyu Cao, Congjie Zhang, Junjing Gu, Yirong Mo

{"title":"双硼杂环烯：Diels-Alder 反应的计算研究","authors":"Changyu Cao, Congjie Zhang, Junjing Gu, Yirong Mo","doi":"10.1039/d4cp03615h","DOIUrl":null,"url":null,"abstract":"Aromatic boron-containing organic compound C2B2H2 with an unusual C=C bond was experimentally synthesized in 2017. Here we investigate the structure and bonding nature of C2B2H2 and its derivatives C2B2R2 using DFT and VB theory. While the C=C bond in C2B2R2 consists of a π bond and a charge-shift (CS) bond, C2B2F2 has the lowest LUMO energy and its LUMO is similar with that of ethylene, suggesting that C2B2F2 can be an ideal dienophile for the Diels-Alder reaction. Subsequently, the mechanism and stereoselectivity of the Diels-Alder reaction of C2B2F2 with 5-substituted cyclopentadienes are studied. Computations demonstrate that these Diels-Alder reactions are feasible thermodynamically and kinetically. The stereoselectivity and distortion angles of C2B2R2 exhibit linear correlations with the electronegativity difference between the two substituents bonded to the C(sp3) of cyclopentadiene, suggesting that the stereoselectivity of related Diels-Alder reaction products can be modulated by the substitution of cyclopentadiene. Considering the current interests in boron neutron capture therapy (BNCT), we design six BNCT drugs through the Diels-Alder reaction of C2B2F2 with dienes containing peptide fragments. Thus, we demonstrate a kind of new method of designing three-in-one BNCT drugs with the facile Diels-Alder reaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Double-Boron Heterocyclic Carbenes: Computational Study of the Diels-Alder Reactions\",\"authors\":\"Changyu Cao, Congjie Zhang, Junjing Gu, Yirong Mo\",\"doi\":\"10.1039/d4cp03615h\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Aromatic boron-containing organic compound C2B2H2 with an unusual C=C bond was experimentally synthesized in 2017. Here we investigate the structure and bonding nature of C2B2H2 and its derivatives C2B2R2 using DFT and VB theory. While the C=C bond in C2B2R2 consists of a π bond and a charge-shift (CS) bond, C2B2F2 has the lowest LUMO energy and its LUMO is similar with that of ethylene, suggesting that C2B2F2 can be an ideal dienophile for the Diels-Alder reaction. Subsequently, the mechanism and stereoselectivity of the Diels-Alder reaction of C2B2F2 with 5-substituted cyclopentadienes are studied. Computations demonstrate that these Diels-Alder reactions are feasible thermodynamically and kinetically. The stereoselectivity and distortion angles of C2B2R2 exhibit linear correlations with the electronegativity difference between the two substituents bonded to the C(sp3) of cyclopentadiene, suggesting that the stereoselectivity of related Diels-Alder reaction products can be modulated by the substitution of cyclopentadiene. Considering the current interests in boron neutron capture therapy (BNCT), we design six BNCT drugs through the Diels-Alder reaction of C2B2F2 with dienes containing peptide fragments. Thus, we demonstrate a kind of new method of designing three-in-one BNCT drugs with the facile Diels-Alder reaction.\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-10-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4cp03615h\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp03615h","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

摘要

2017 年，实验合成了具有不寻常 C=C 键的芳香族含硼有机化合物 C2B2H2。在此，我们利用 DFT 和 VB 理论研究了 C2B2H2 及其衍生物 C2B2R2 的结构和成键性质。C2B2R2中的C=C键由一个π键和一个电荷转移（CS）键组成，而C2B2F2的LUMO能最低，其LUMO与乙烯的LUMO相近，这表明C2B2F2可以成为Diels-Alder反应的理想亲二烯。随后，研究了 C2B2F2 与 5 取代环戊二烯的 Diels-Alder 反应机理和立体选择性。计算表明，这些 Diels-Alder 反应在热力学和动力学上都是可行的。C2B2R2 的立体选择性和畸变角与环戊二烯 C(sp3)键上两个取代基之间的电负性差异呈线性相关，这表明相关 Diels-Alder 反应产物的立体选择性可以通过环戊二烯的取代来调节。考虑到目前人们对硼中子俘获疗法（BNCT）的兴趣，我们通过 C2B2F2 与含有肽片段的二烯的 Diels-Alder 反应设计了六种 BNCT 药物。因此，我们展示了一种利用简便的 Diels-Alder 反应设计三合一 BNCT 药物的新方法。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Double-Boron Heterocyclic Carbenes: Computational Study of the Diels-Alder Reactions

Aromatic boron-containing organic compound C₂B₂H₂ with an unusual C=C bond was experimentally synthesized in 2017. Here we investigate the structure and bonding nature of C₂B₂H₂ and its derivatives C₂B₂R₂ using DFT and VB theory. While the C=C bond in C₂B₂R₂ consists of a π bond and a charge-shift (CS) bond, C₂B₂F₂ has the lowest LUMO energy and its LUMO is similar with that of ethylene, suggesting that C₂B₂F₂ can be an ideal dienophile for the Diels-Alder reaction. Subsequently, the mechanism and stereoselectivity of the Diels-Alder reaction of C₂B₂F₂ with 5-substituted cyclopentadienes are studied. Computations demonstrate that these Diels-Alder reactions are feasible thermodynamically and kinetically. The stereoselectivity and distortion angles of C₂B₂R₂ exhibit linear correlations with the electronegativity difference between the two substituents bonded to the C(sp³) of cyclopentadiene, suggesting that the stereoselectivity of related Diels-Alder reaction products can be modulated by the substitution of cyclopentadiene. Considering the current interests in boron neutron capture therapy (BNCT), we design six BNCT drugs through the Diels-Alder reaction of C₂B₂F₂ with dienes containing peptide fragments. Thus, we demonstrate a kind of new method of designing three-in-one BNCT drugs with the facile Diels-Alder reaction.

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

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.