Palladium-Catalyzed Direct B—H Oxygenation:Facile Synthesis of o-Carboranofuranones  

作　　者：Chenyang Guo Zaozao Qiu Zuowei Xie 

机构地区：[1]Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,345 Lingling Rd.,Shanghai 200032,China [2]International Joint Laboratory of Catalytic Chemistry,epartmentof Chemistry,Cllegeof Sciences,Shanghai Universit Shanghai 200444,China [3]Shenzhen Grubbs Institute and Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong 518055,China

出　　处：《Chinese Journal of Chemistry》2024年第23期3083-3087,共5页中国化学(英文版)

基　　金：supported by the grants from the National Natural Science Foundation of China(Project Nos.22371290 and 92056106 to Z.Q.,Project No.22331005 to Z.X.);Shenzhen Science and Technology Program(Project No.QTD20221101093558015 to Z.X.);the Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis,CAS.

摘　　要：Recent advances in transition metal-catalyzed o-carborane B—H activation have led to the rapid development of various methodologies for cage boron functionalization.For catalytic cage B—H acyloxylation,intermolecular oxygenation gave products with different regioselectivities(B(3)-,B(4)-,and B(8,9)-selectivities).Herein,an efficient palladium-catalyzed direct cage B(4)–H oxygenation of o-carboranylacetic acids has been achieved,where the carboxylic group serves as not only a directing group,but also a coupling partner.A wide range of substituted o-carboranylacetic acids have been cyclized via the formation of B(4)−O bond to give the corresponding γ-lactones in modest to excellent yields.A Pd(Ⅳ)intermediate is proposed to be involved in the catalytic cycle.This work offers valuable references for the BH/OH dehydrocoupling reactions under mild conditions to produce carborane-featuring functional molecules.

关 键 词：CARBORANE B-H activation OXYGENATION Catalysis Transition metal Palladium Cross-coupling Regioselectivity 

分 类 号：O62[理学—有机化学]