金(I)催化四氢二氮卓类或四氢二氮卓类烯烯的区域发散氢化芳基化反应

IF 4.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis Pub Date : 2025-01-14 DOI:10.1002/adsc.202401541

Pengyu Zhou, pascal retailleau, Vincent Gandon, Arnaud Voituriez, Xavier Guinchard

{"title":"金(I)催化四氢二氮卓类或四氢二氮卓类烯烯的区域发散氢化芳基化反应","authors":"Pengyu Zhou, pascal retailleau, Vincent Gandon, Arnaud Voituriez, Xavier Guinchard","doi":"10.1002/adsc.202401541","DOIUrl":null,"url":null,"abstract":"Allenes tethered to pyrroles undergo Au(I)-catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl-gem-disubstituted allenes preferentially lead to tetrahydrodiazepines via 7-exo- cyclizations, while aryl-substituted allenes preferentially lead to tetrahydrodiazonines via 9-endo cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7-exo vs 9-endo) of these gold(I)-catalyzed cyclizations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"20 1","pages":""},"PeriodicalIF":4.4000,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Au(I)-Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines\",\"authors\":\"Pengyu Zhou, pascal retailleau, Vincent Gandon, Arnaud Voituriez, Xavier Guinchard\",\"doi\":\"10.1002/adsc.202401541\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Allenes tethered to pyrroles undergo Au(I)-catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl-gem-disubstituted allenes preferentially lead to tetrahydrodiazepines via 7-exo- cyclizations, while aryl-substituted allenes preferentially lead to tetrahydrodiazonines via 9-endo cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7-exo vs 9-endo) of these gold(I)-catalyzed cyclizations.\",\"PeriodicalId\":118,\"journal\":{\"name\":\"Advanced Synthesis & Catalysis\",\"volume\":\"20 1\",\"pages\":\"\"},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2025-01-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Synthesis & Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/adsc.202401541\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Synthesis & Catalysis","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/adsc.202401541","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}

引用次数: 0

摘要

连接到吡咯上的烯经过Au(I)催化的氢化芳基化反应生成四氢二氮卓类或四氢二氮卓类化合物。反应的区域选择性由烯的取代模式和Au(I)配体的性质共同决定。因此，当使用亚磷酸盐配体时，烷基基双取代烯优先通过7-外环化生成四氢二氮卓类化合物，而芳基取代烯优先通过9-内环化生成四氢重氮类化合物。与SEGPHOS手性配体发生了对映选择性反应，产生了具有高对映选择性（高达96% ee）的手性杂环。此外，DFT计算简化了这些金(I)催化的环化反应的区域选择性（7-exo vs 9-endo）。

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

Au(I)-Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines

Allenes tethered to pyrroles undergo Au(I)-catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl-gem-disubstituted allenes preferentially lead to tetrahydrodiazepines via 7-exo- cyclizations, while aryl-substituted allenes preferentially lead to tetrahydrodiazonines via 9-endo cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7-exo vs 9-endo) of these gold(I)-catalyzed cyclizations.

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

Advanced Synthesis & Catalysis 化学-应用化学

CiteScore

9.40

自引率

7.40%

发文量

447

审稿时长

1.8 months

期刊介绍： Advanced Synthesis & Catalysis (ASC) is the leading primary journal in organic, organometallic, and applied chemistry. The high impact of ASC can be attributed to the unique focus of the journal, which publishes exciting new results from academic and industrial labs on efficient, practical, and environmentally friendly organic synthesis. While homogeneous, heterogeneous, organic, and enzyme catalysis are key technologies to achieve green synthesis, significant contributions to the same goal by synthesis design, reaction techniques, flow chemistry, and continuous processing, multiphase catalysis, green solvents, catalyst immobilization, and recycling, separation science, and process development are also featured in ASC. The Aims and Scope can be found in the Notice to Authors or on the first page of the table of contents in every issue.