{"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 C<small><sub>2</sub></small>B<small><sub>2</sub></small>H<small><sub>2</sub></small> with an unusual C=C bond was experimentally synthesized in 2017. Here we investigate the structure and bonding nature of C<small><sub>2</sub></small>B<small><sub>2</sub></small>H<small><sub>2</sub></small> and its derivatives C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> using DFT and VB theory. While the C=C bond in C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> consists of a π bond and a charge-shift (CS) bond, C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> has the lowest LUMO energy and its LUMO is similar with that of ethylene, suggesting that C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> can be an ideal dienophile for the Diels-Alder reaction. Subsequently, the mechanism and stereoselectivity of the Diels-Alder reaction of C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> with 5-substituted cyclopentadienes are studied. Computations demonstrate that these Diels-Alder reactions are feasible thermodynamically and kinetically. The stereoselectivity and distortion angles of C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> exhibit linear correlations with the electronegativity difference between the two substituents bonded to the C(sp<small><sup>3</sup></small>) 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 C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> 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 C<small><sub>2</sub></small>B<small><sub>2</sub></small>H<small><sub>2</sub></small> with an unusual C=C bond was experimentally synthesized in 2017. Here we investigate the structure and bonding nature of C<small><sub>2</sub></small>B<small><sub>2</sub></small>H<small><sub>2</sub></small> and its derivatives C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> using DFT and VB theory. While the C=C bond in C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> consists of a π bond and a charge-shift (CS) bond, C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> has the lowest LUMO energy and its LUMO is similar with that of ethylene, suggesting that C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> can be an ideal dienophile for the Diels-Alder reaction. Subsequently, the mechanism and stereoselectivity of the Diels-Alder reaction of C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> with 5-substituted cyclopentadienes are studied. Computations demonstrate that these Diels-Alder reactions are feasible thermodynamically and kinetically. The stereoselectivity and distortion angles of C<small><sub>2</sub></small>B<small><sub>2</sub></small>R<small><sub>2</sub></small> exhibit linear correlations with the electronegativity difference between the two substituents bonded to the C(sp<small><sup>3</sup></small>) 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 C<small><sub>2</sub></small>B<small><sub>2</sub></small>F<small><sub>2</sub></small> 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}
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.
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.
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