{"title":"Split cross-coupling via Rh-catalysed activation of unstrained aryl–aryl bonds","authors":"Congjun Yu, Zining Zhang, Guangbin Dong","doi":"10.1038/s41929-024-01120-9","DOIUrl":null,"url":null,"abstract":"Constructive functionalization of unstrained aryl–aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows twofold arylation with diverse aryl iodides through cleaving unstrained aryl–aryl bonds of common 2,2′-biphenols. The reaction is catalysed by a rhodium complex and promoted by a removable phosphinite directing group and an organic reductant such as tetrakis(dimethylamino)ethylene. The combined experimental and computational mechanistic studies reveal a turnover-limiting reductive elimination step that can be accelerated by a Lewis acid co-catalyst. The utility of this coupling method has been illustrated in the modular and simplified syntheses of unsymmetrical 2,6-diarylated phenols and skeletal insertion of phenylene units. Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8000,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.nature.com/articles/s41929-024-01120-9","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Constructive functionalization of unstrained aryl–aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows twofold arylation with diverse aryl iodides through cleaving unstrained aryl–aryl bonds of common 2,2′-biphenols. The reaction is catalysed by a rhodium complex and promoted by a removable phosphinite directing group and an organic reductant such as tetrakis(dimethylamino)ethylene. The combined experimental and computational mechanistic studies reveal a turnover-limiting reductive elimination step that can be accelerated by a Lewis acid co-catalyst. The utility of this coupling method has been illustrated in the modular and simplified syntheses of unsymmetrical 2,6-diarylated phenols and skeletal insertion of phenylene units. Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.
期刊介绍:
Nature Catalysis serves as a platform for researchers across chemistry and related fields, focusing on homogeneous catalysis, heterogeneous catalysis, and biocatalysts, encompassing both fundamental and applied studies. With a particular emphasis on advancing sustainable industries and processes, the journal provides comprehensive coverage of catalysis research, appealing to scientists, engineers, and researchers in academia and industry.
Maintaining the high standards of the Nature brand, Nature Catalysis boasts a dedicated team of professional editors, rigorous peer-review processes, and swift publication times, ensuring editorial independence and quality. The journal publishes work spanning heterogeneous catalysis, homogeneous catalysis, and biocatalysis, covering areas such as catalytic synthesis, mechanisms, characterization, computational studies, nanoparticle catalysis, electrocatalysis, photocatalysis, environmental catalysis, asymmetric catalysis, and various forms of organocatalysis.