Palladium-Catalyzed Regioselective Asymmetric Chemodivergent Allylation of Oxazolones with Morita-Baylis-Hillman Adducts

作     者：Rui Zhang Zibo Liu Yong Liu Haoran Yang Xiaoming Wang Zhaobin Han Zheng Wang Kuiling Ding 

作者机构：State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryChinese Academy of SciencesUniversity of Chinese Academy of SciencesShanghai 200032 School of Physical Science and TechnologyShanghaiTech UniversityShanghai 201210 Frontiers Science Center for Transformative MoleculesSchool of Chemistry and Chemical EngineeringShanghai Jiao Tong UniversityShanghai 200240 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2023年第5卷第12期

页      面：2790-2798页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：financial supports from the National Key R&D Program of China(grant nos.2022YFA1503702 and 2021YFF0701602) NSFC(grant nos.22231011 and 22271303) 

主　　题：asymmetric catalysis allylic alkylation palladium oxazolones chemodivergent 

摘      要：Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological ***,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylation of 4-or 5-substituted oxazol-2(3H)-ones with Morita-Baylis-Hillman(MBH)adducts has been developed using a spiroketal-based diphosphine as the ligand(50 examples).Interestingly,4-substituted oxazol-2(3H)-ones acted as a C-nucleophiles in the reaction to afford a range of chiral 4,5-substituted oxazol-2(3H)-ones in high yields(72-99%)with good to excellent chemo-,regio-,and enantioselectivities(C/N 95:5-99:1,b/l 91:9-99:1,85-98%ee).When a N-nucleophile was used under otherwise identical conditions,5-substituted oxazol-2(3H)-ones delivered a range of chiral 3,5-substituted oxazol-2(3H)-ones in high yields(68-98%)with good regio-and enantioselectivities(b/l 71:29-91:9,66-94%ee).The synthesis can be readily performed on gram scale under fairly low catalyst loadings,and the utility of the protocol was showcased in the facile transformation of the products into more elaborate chiral molecules.