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 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,University of Chinese Academy of Sciences,Shanghai 200032 [2]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210 [3]Frontiers Science Center for Transformative Molecules,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2023年第12期2790-2798,共9页中国化学会会刊（英文）

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

摘　　要：Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,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.

关 键 词：asymmetric catalysis allylic alkylation palladium OXAZOLONES chemodivergent 

分 类 号：O62[理学—有机化学]