{"title":"利用单膦钴乙酰配合物,高效地将环氧化物羰基化成β-内酯","authors":"Vinothkumar Ganesan, Senkuttuvan Rajendiran, Jianwei Jiang, Sungho Yoon","doi":"10.1016/j.jcat.2025.116381","DOIUrl":null,"url":null,"abstract":"<div><div>The carbonylation of epoxides to β-lactones offers a direct and efficient pathway to valuable synthetic intermediates. However, the development of cost-effective and robust catalysts capable of delivering high turnover numbers (TONs) under mild conditions remains a significant challenge. In this study, a monodentate phosphine-ligated cobalt acetyl complex in combination with tetraphenyl porphyrin chromium(III) chloride (TPPCrCl), {[Co(acetyl)(CO)<sub>3</sub>(PPh<sub>3</sub>)]/[TPPCrCl]} (1), was optimized to catalyze epoxide carbonylation under mild conditions (30 °C, 1 bar CO), achieving > 99.9 % selectivity toward β-lactone formation. Under conditions of high substrate-to-catalyst ratios and elevated temperature, catalyst 1 exhibited exceptional stability and delivered a record TON of 195,600, demonstrating its strong potential for scalable β-lactone production.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116381"},"PeriodicalIF":6.5000,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Highly efficient epoxide carbonylation to β-lactones using a monophosphine cobalt acetyl complex\",\"authors\":\"Vinothkumar Ganesan, Senkuttuvan Rajendiran, Jianwei Jiang, Sungho Yoon\",\"doi\":\"10.1016/j.jcat.2025.116381\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The carbonylation of epoxides to β-lactones offers a direct and efficient pathway to valuable synthetic intermediates. However, the development of cost-effective and robust catalysts capable of delivering high turnover numbers (TONs) under mild conditions remains a significant challenge. In this study, a monodentate phosphine-ligated cobalt acetyl complex in combination with tetraphenyl porphyrin chromium(III) chloride (TPPCrCl), {[Co(acetyl)(CO)<sub>3</sub>(PPh<sub>3</sub>)]/[TPPCrCl]} (1), was optimized to catalyze epoxide carbonylation under mild conditions (30 °C, 1 bar CO), achieving > 99.9 % selectivity toward β-lactone formation. Under conditions of high substrate-to-catalyst ratios and elevated temperature, catalyst 1 exhibited exceptional stability and delivered a record TON of 195,600, demonstrating its strong potential for scalable β-lactone production.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"451 \",\"pages\":\"Article 116381\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-08-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951725004476\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951725004476","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
环氧化物羰基化生成β-内酯为合成有价值的中间体提供了一条直接有效的途径。然而,开发在温和条件下能够提供高周转率(吨)的高成本效益和强大的催化剂仍然是一个重大挑战。在本研究中,优化了单齿膦连接的钴乙酰基配合物与四苯基卟啉氯化铬(TPPCrCl)结合,{[Co(acetyl)(Co)3(PPh3)]/[TPPCrCl]}(1),在温和条件下(30℃,1 bar Co)催化环氧化物羰基化,对β-内酯生成的选择性达到99.9%。在高底物-催化剂比和高温条件下,催化剂1表现出了优异的稳定性,并创造了195,600吨的记录,显示了其在可扩展β-内酯生产方面的强大潜力。
Highly efficient epoxide carbonylation to β-lactones using a monophosphine cobalt acetyl complex
The carbonylation of epoxides to β-lactones offers a direct and efficient pathway to valuable synthetic intermediates. However, the development of cost-effective and robust catalysts capable of delivering high turnover numbers (TONs) under mild conditions remains a significant challenge. In this study, a monodentate phosphine-ligated cobalt acetyl complex in combination with tetraphenyl porphyrin chromium(III) chloride (TPPCrCl), {[Co(acetyl)(CO)3(PPh3)]/[TPPCrCl]} (1), was optimized to catalyze epoxide carbonylation under mild conditions (30 °C, 1 bar CO), achieving > 99.9 % selectivity toward β-lactone formation. Under conditions of high substrate-to-catalyst ratios and elevated temperature, catalyst 1 exhibited exceptional stability and delivered a record TON of 195,600, demonstrating its strong potential for scalable β-lactone production.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.