报告题目：Metathesis of Fluoroalkenes: Synthesis & Applications

报 告 人：Dr. Samuel COUVE-BONNAIRE

报告人单位：法国鲁昂国立应用科学院（INSA Rouen Normandie）

报告时间：2023年12月12日 上午10: 00

报告地点：杭州师范大学仓前校区，勤园22号楼402室

报告邀请人：叶飞 副教授

报告人介绍：

Samuel COUVE-BONNAIRE博士，副教授，法国鲁昂国立应用科学学院 “Fluorinated Biomolecules team”研究员。他于2001年在法国里尔大学获得博士学位，导师为Y. Castanet教授和J.-F. Carpentier教授，均相催化部分导师为A. Mortreux教授。2002年至2003年，在加拿大国家研究院资助下于渥太华Steacie分子科学研究所P. Arya课题组从事博士后研究。2003年至2005年，作为工业合作伙伴完成了SANOFI-AVENTIS的博士后研究。2005年进入法国鲁昂国立应用科学学院开展独立研究工作。目前，他的研究方向集中在开发新的有机合成方法学，主要包括：自由基化学或有机金属反应（如复分解、C-H键官能化或交叉偶联反应）构建氟化烯烃及其在生物化学上的应用等等。Samuel COUVE-BONNAIRE教授已在包括ACS Catal., J. Org. Chem., Org. Lett.等国际著名学术期刊发表约50篇研究论文，受邀参与9场学术报告，在有机化学领域有一定的影响力。

Abstract:

Whereas the olefin metathesis is recognized as a powerful tool to produce alkene, the use of fluoroalkenes in metathesis catalyzed-reactions still remains a major current challenge. First, I will present a challenging homogeneous Ring-Closing Metathesis reaction with reluctant fluorinated substrates. The use of fluorinated aromatic hydrocarbons (FAH) and appropriate substitution of the double bonds allowed to reach almost quantitative yields for the formation of new relevant five-, six-and seven-membered rings. Application towards peptidomimetics will be highlighted. Second, I will present the result obtained in Cross-Metathesis (CM) process, which is scarcely described with fluororalkenes. Using the methyl 2-fluoroacrylate as easy accessible, convenient, reactive and post-functionalizable source of fluoroalkene, we developed an efficient ruthenium-catalyzed CM reaction of various terminal and internal alkenes giving access, for the first time, to trisubstituted fluoroalkenes stereoselectively. Unprecedent TON for CM involving fluoroalkene, up to 175, have been obtained and the reaction give fair to high yields in cross-metathesis products.

代表性论文：

(1) Morand, S.; Lecroq, W.; Jubault, P.; Lakhdar, S.; Bouillon, J.-P.; Couve-Bonnaire S. Organophotocatalysis Enables the Synthesis of gem-Fluorophosphonate Alkenes. Org. Lett. 2022, 24, 8343−8347;

(2) Huang, X.; Besset, T.; Jubault, P.; Couve-Bonnaire, S. Phospha-Michael addition on α-fluorinated acrylates: a straightforward access to polyfunctionalized fine chemicals. J. Org. Chem. 2022, 87, 9210−9221;

(3) Nouaille, A.; Lorkowski, J.; Pannecoucke, X.; Mauduit, M.; Poisson, T.; Couve-Bonnaire, S. Metal-Catalyzed Metathesis of Fluorinated Alkenes: still a current major challenge. ACS Catal. 2021, 11, 12307-12323;

(4) Xiao, P.; Pannecoucke, X.; Bouillon, J.-P.; CouveBonnaire, S. Ligand Free Palladium-catalyzed Synthesis of α-Trifluoromethylacrylic Acids and Related Acrylates by Three-component Reaction. Adv. Synth. Catal. 2020, 362, 949-954;

(5) Petit-Cancelier, F.; François, B.; Pannecoucke, X.; Couve-Bonnaire, S.; Besset, T. S-(Diethyl phosphonodifluoromethyl)Benzenesulfonothioate: A New Reagent for the Synthesis of SCF₂PO(OEt)₂-containing Molecules. Adv. Synth. Catal. 2020, 362, 760-764.