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Auto‐Tandem Cooperative Catalysis Using Phosphine/Palladium: Reaction of Morita–Baylis–Hillman Carbonates and Allylic Alcohols
Author(s) -
Chen Peng,
Chen ZhiChao,
Li Yue,
Ouyang Qin,
Du Wei,
Chen YingChun
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814403
Subject(s) - phosphine , allylic rearrangement , chemistry , tsuji–trost reaction , catalysis , regioselectivity , palladium , intramolecular force , heck reaction , cascade reaction , tandem , combinatorial chemistry , organic chemistry , medicinal chemistry , materials science , composite material
Auto‐tandem catalysis (ATC), in which a single catalyst promotes two or more mechanistically different reactions in a cascade pattern, provides a powerful strategy to prepare complex products from simple starting materials. Reported here is an unprecedented auto‐tandem cooperative catalysis (ATCC) for Morita–Baylis–Hillman carbonates from isatins and allylic carbonates using a simple Pd(PPh 3 ) 4 precursor. Dissociated phosphine generates phosphorus ylides and the Pd leads to π‐allylpalladium complexes, and they undergo a γ‐regioselective allylic–allylic alkylation reaction. Importantly, a cascade intramolecular Heck‐type coupling proceeds to finally furnish spirooxindoles incorporating a 4‐methylene‐2‐cyclopentene motif. Experimental results indicate that both Pd and phosphine play crucial roles in the catalytic Heck reaction. In addition, the asymmetric versions with either a chiral phosphine or chiral auxiliary are explored, and moderate results are obtained.