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Allylic Acetals as Acrolein Oxonium Precursors in Tandem C−H Allylation and [3+2] Dipolar Cycloaddition
Author(s) -
Lee Heeyoung,
Kang Dahye,
Han Sang Hoon,
Chun Rina,
Pandey Ashok Kumar,
Mishra Neeraj Kumar,
Hong Sungwoo,
Kim In Su
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.201903983
Subject(s) - allylic rearrangement , cycloaddition , chemistry , oxonium ion , tandem , surface modification , azomethine ylide , 1,3 dipolar cycloaddition , quenching (fluorescence) , combinatorial chemistry , catalysis , stereochemistry , organic chemistry , ion , materials science , composite material , physics , quantum mechanics , fluorescence
Abstract The ruthenium(II)‐catalyzed C−H functionalization of (hetero)aryl azomethine imines with allylic acetals is described. The initial formation of allylidene(methyl)oxoniums from allylic acetals could trigger C(sp 2 )−H allylation, and subsequent endo ‐type [3+2] dipolar cycloaddition of polar azomethine fragments to deliver valuable indenopyrazolopyrazolones. The utility of this method is showcased by the late‐stage functionalization of bioactive molecules such as estrone and celecoxib. Combined experimental and computational investigations elucidate a plausible mechanism of this new tandem reaction. Notably, the reductive transformation of synthesized compounds into biologically relevant diazocine frameworks highlights the importance of the developed methodology.