2024-03-29T10:12:05Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:02001675
2023-01-16T05:06:53Z
1903:1904:1905
1,2‐Carbopentafluorophenylation of Alkynes: The Metallomimetic Pull‐Push Reactivity of Tris(pentafluorophenyl)borane
Shibuya, Masatoshi
Matsuda, Miki
Yamamoto, Yoshihiko
open access
"This is the peer reviewed version of the following article: [M. Shibuya, M. Matsuda, Y. Yamamoto, Chem. Eur. J. 2021, 27, 8822.], which has been published in final form at [https://doi.org/10.1002/chem.202101090]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited."
We report the novel single-step 1,2-dicarbofunctionalization of an arylacetylene with an allylsilane and tris(pentafluorophenyl)borane [B(C6F5)3] involving C−C bond formation with C−H bond scission at the β-position to the silicon atom of an allylsilane and B→C migration of a C6F5 group. The 1,2-carbopentafluorophenylation occurs smoothly without the requirement for a catalyst or heating. Mechanistic studies suggest that the metallomimetic “pull-push” reactivity of B(C6F5)3 imparts consecutive electrophilic and nucleophilic characteristics to the benzylic carbon of the arylacetylene. Subsequent photochemical 6π-electrocyclization affords tetrafluoronaphthalenes, which are important in the pharmaceutical and materials sciences. Owing to the unique reactivity of B(C6F5)3, the 1,2-carbopentafluorophenylation using 2-substituted furan proceeded with ring opening, and the reaction using silyl enolates formed a C−C bond with C−O bond scission at the silyloxy-substituted carbon.
Wiley
2022-06-16
2021-06-16
eng
journal article
AM
http://hdl.handle.net/2237/0002001675
https://nagoya.repo.nii.ac.jp/records/2001675
https://doi.org/10.1002/chem.202101090
0947-6539
Chemistry – A European Journal
27
34
8822
8831
https://nagoya.repo.nii.ac.jp/record/2001675/files/CEJ2021.pdf
application/pdf
1.5 MB
2022-06-16