Boliang Dong, Teng Wang, Gang Gao, Xiaolong Zhang, Ying He
{"title":"环丙酚的实用和可扩展生产工艺的发展","authors":"Boliang Dong, Teng Wang, Gang Gao, Xiaolong Zhang, Ying He","doi":"10.1021/acs.oprd.5c00044","DOIUrl":null,"url":null,"abstract":"Ciprofol is a novel clinical anesthetic and is deemed a better alternative to propofol due to its fewer side effects. Herein, we report an atom-economical and cost-efficient manufacturing process to prepare Ciprofol, which includes regioselective <i>para</i>-halogenation of phenol, followed by esterification and Fries rearrangement in high yields. This strategy adopts <i>para</i>-halogenation to avoid the generation of <i>para</i>-byproducts in the Fries rearrangement. After a benign reduction of bromine and the Wittig reaction, the desired Ciprofol is achieved by ruthenium-catalyzed asymmetric hydrogenation. This new process has been tested on a multigram scale, with an improved overall yield of 60% and enhanced cost efficiency, while offering atom economy advantages. The low yield of the Claisen rearrangement and the use of costly and corrosive reagents in the previously reported synthesis were avoided.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"85 1","pages":""},"PeriodicalIF":3.1000,"publicationDate":"2025-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Development of a Practical and Scalable Manufacturing Process for Ciprofol\",\"authors\":\"Boliang Dong, Teng Wang, Gang Gao, Xiaolong Zhang, Ying He\",\"doi\":\"10.1021/acs.oprd.5c00044\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Ciprofol is a novel clinical anesthetic and is deemed a better alternative to propofol due to its fewer side effects. Herein, we report an atom-economical and cost-efficient manufacturing process to prepare Ciprofol, which includes regioselective <i>para</i>-halogenation of phenol, followed by esterification and Fries rearrangement in high yields. This strategy adopts <i>para</i>-halogenation to avoid the generation of <i>para</i>-byproducts in the Fries rearrangement. After a benign reduction of bromine and the Wittig reaction, the desired Ciprofol is achieved by ruthenium-catalyzed asymmetric hydrogenation. This new process has been tested on a multigram scale, with an improved overall yield of 60% and enhanced cost efficiency, while offering atom economy advantages. The low yield of the Claisen rearrangement and the use of costly and corrosive reagents in the previously reported synthesis were avoided.\",\"PeriodicalId\":55,\"journal\":{\"name\":\"Organic Process Research & Development\",\"volume\":\"85 1\",\"pages\":\"\"},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2025-04-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Process Research & Development\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.oprd.5c00044\",\"RegionNum\":3,\"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":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.oprd.5c00044","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Development of a Practical and Scalable Manufacturing Process for Ciprofol
Ciprofol is a novel clinical anesthetic and is deemed a better alternative to propofol due to its fewer side effects. Herein, we report an atom-economical and cost-efficient manufacturing process to prepare Ciprofol, which includes regioselective para-halogenation of phenol, followed by esterification and Fries rearrangement in high yields. This strategy adopts para-halogenation to avoid the generation of para-byproducts in the Fries rearrangement. After a benign reduction of bromine and the Wittig reaction, the desired Ciprofol is achieved by ruthenium-catalyzed asymmetric hydrogenation. This new process has been tested on a multigram scale, with an improved overall yield of 60% and enhanced cost efficiency, while offering atom economy advantages. The low yield of the Claisen rearrangement and the use of costly and corrosive reagents in the previously reported synthesis were avoided.
期刊介绍:
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools,process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.