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Unusual 1,2-Aryl Migration and Depalladation of Alkylpalladium Intermediates Containing a syn-beta-Hydrogen Atom

Title
Unusual 1,2-Aryl Migration and Depalladation of Alkylpalladium Intermediates Containing a syn-beta-Hydrogen Atom
Author
윤소원
Keywords
1,2-aryl migration; cyclization; palladium; rearrangement
Issue Date
2016-11
Publisher
WILEY-V C H VERLAG GMBH
Citation
CHEMISTRYSELECT, v. 1, Issue 18, Page. 5749-5757
Abstract
In general, alkylpalladium intermediates containing a syn beta-hydrogen atom are expected to undergo beta-hydride elimination preferentially. However, this study unveils a new mechanistic mode in a Pd(II)-catalyzed transformation, which leads to a series of both C-N/C-C bond forming and C-C bond forming/cleavage events. It has been demonstrated that a Pd(II)catalyzed oxidative cyclization of stilbenes bearing a pendent nucleophile such as 2-alkenylanilines and 2-alkenylphenyl 1,3-diketones operates through an uncommon Pd-C bond cleavage assisted by a neighboring aryl group and CuCl2-assisted transient Pd oxidation, rather than generally preferred beta-hydride elimination in alkylpalladium intermediates containing a syn beta-hydrogen atom. As a result, 1,2-aryl migration occurs to lead to the unexpected formation of a variety of 3-substituted indoles and 4-aryl-1-naphthols. In addition, selective migration of an aryl group could be achieved from beta,beta-disubstituted alkene substrates through alkylpalladium intermediates deprived of syn beta-hydrogen atom.
URI
https://onlinelibrary.wiley.com/doi/full/10.1002/slct.201601382https://repository.hanyang.ac.kr/handle/20.500.11754/101191
ISSN
2365-6549
DOI
10.1002/slct.201601382
Appears in Collections:
COLLEGE OF NATURAL SCIENCES[S](자연과학대학) > CHEMISTRY(화학과) > Articles
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