Congcong Huang, Biyao Yang, Keying Zhang and Juan Li
{"title":"铜/钌接力催化 1,4-不相邻立体中心的立体异构:利用 DFT 计算进行机理研究","authors":"Congcong Huang, Biyao Yang, Keying Zhang and Juan Li","doi":"10.1039/D4QO00780H","DOIUrl":null,"url":null,"abstract":"<p >Recent research has developed a Cu/Ru dual catalysis system for the hydroalkylation of racemic allylic alcohols and racemic ketimine esters. This method is distinguished by its ability to stereodivergently generate 1,4-nonadjacent stereocenters. This study employs density functional theory calculations to elucidate how copper and ruthenium synergistically drive this transformation and to reveal why this dual-catalyst system is more efficient than systems using either copper or ruthenium independently. The findings show how different combinations of chiral catalysts influence the formation of two stereogenic centers. We highlight the critical roles of noncovalent interactions and steric effects in determining the most energetically favorable transition states for each catalyst combination. Additionally, this study elucidates the significant role of potassium phosphate (K<small><sub>3</sub></small>PO<small><sub>4</sub></small>) in enhancing the reaction efficiency. Specifically, K<small><sub>3</sub></small>PO<small><sub>4</sub></small> facilitates the dehydrogenation and hydrogenation processes across all three stages of the catalytic cycle. We also explore the reaction's chemoselectivity by computing the formation mechanisms of three potential by-products and analyzing the driving forces behind the generation of the desired product. These mechanistic insights can support advancements in stereodivergent synthesis using cooperative bimetallic catalysis.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Copper/ruthenium relay catalysis for stereodivergent construction of 1,4-nonadjacent stereocenters: mechanistic investigation using DFT calculations†\",\"authors\":\"Congcong Huang, Biyao Yang, Keying Zhang and Juan Li\",\"doi\":\"10.1039/D4QO00780H\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Recent research has developed a Cu/Ru dual catalysis system for the hydroalkylation of racemic allylic alcohols and racemic ketimine esters. This method is distinguished by its ability to stereodivergently generate 1,4-nonadjacent stereocenters. This study employs density functional theory calculations to elucidate how copper and ruthenium synergistically drive this transformation and to reveal why this dual-catalyst system is more efficient than systems using either copper or ruthenium independently. The findings show how different combinations of chiral catalysts influence the formation of two stereogenic centers. We highlight the critical roles of noncovalent interactions and steric effects in determining the most energetically favorable transition states for each catalyst combination. Additionally, this study elucidates the significant role of potassium phosphate (K<small><sub>3</sub></small>PO<small><sub>4</sub></small>) in enhancing the reaction efficiency. Specifically, K<small><sub>3</sub></small>PO<small><sub>4</sub></small> facilitates the dehydrogenation and hydrogenation processes across all three stages of the catalytic cycle. We also explore the reaction's chemoselectivity by computing the formation mechanisms of three potential by-products and analyzing the driving forces behind the generation of the desired product. These mechanistic insights can support advancements in stereodivergent synthesis using cooperative bimetallic catalysis.</p>\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-06-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00780h\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00780h","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Copper/ruthenium relay catalysis for stereodivergent construction of 1,4-nonadjacent stereocenters: mechanistic investigation using DFT calculations†
Recent research has developed a Cu/Ru dual catalysis system for the hydroalkylation of racemic allylic alcohols and racemic ketimine esters. This method is distinguished by its ability to stereodivergently generate 1,4-nonadjacent stereocenters. This study employs density functional theory calculations to elucidate how copper and ruthenium synergistically drive this transformation and to reveal why this dual-catalyst system is more efficient than systems using either copper or ruthenium independently. The findings show how different combinations of chiral catalysts influence the formation of two stereogenic centers. We highlight the critical roles of noncovalent interactions and steric effects in determining the most energetically favorable transition states for each catalyst combination. Additionally, this study elucidates the significant role of potassium phosphate (K3PO4) in enhancing the reaction efficiency. Specifically, K3PO4 facilitates the dehydrogenation and hydrogenation processes across all three stages of the catalytic cycle. We also explore the reaction's chemoselectivity by computing the formation mechanisms of three potential by-products and analyzing the driving forces behind the generation of the desired product. These mechanistic insights can support advancements in stereodivergent synthesis using cooperative bimetallic catalysis.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.