Unusual 1,2-Aryl Migration and Depalladation of Alkylpalladium Intermediates Containing a syn-beta-Hydrogen Atom
- Authors
- Youn, So Won; Lee, So Ra; Kim, Yun Ah; Kang, Da Young; Jang, Min Jung
- Issue Date
- Nov-2016
- Publisher
- WILEY-V C H VERLAG GMBH
- Keywords
- 1,2-aryl migration; cyclization; palladium; rearrangement
- Citation
- CHEMISTRYSELECT, v.1, no.18, pp.5749 - 5757
- Indexed
- SCIE
SCOPUS
- Journal Title
- CHEMISTRYSELECT
- Volume
- 1
- Number
- 18
- Start Page
- 5749
- End Page
- 5757
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/153645
- DOI
- 10.1002/slct.201601382
- ISSN
- 2365-6549
- 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.
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