Palladium-Catalyzed para-Selective Allylation of 1-(Cyanomethyl)arenes with Allyl Acetates

Rina Muto; Kenji Nagata; Yoshiki Nakazumi; Kaho Nakamura; Satoshi Ueno

doi:10.1021/acs.orglett.3c00534

Palladium-Catalyzed para-Selective Allylation of 1-(Cyanomethyl)arenes with Allyl Acetates

Org Lett. 2023 Mar 31;25(12):2108-2112. doi: 10.1021/acs.orglett.3c00534. Epub 2023 Mar 20.

Authors

Rina Muto¹, Kenji Nagata¹, Yoshiki Nakazumi¹, Kaho Nakamura¹, Satoshi Ueno¹

Affiliation

¹ Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Technology, 1404-1 Katakura, Hachioji, Tokyo 192-0982, Japan.

PMID: 36940090
DOI: 10.1021/acs.orglett.3c00534

Abstract

The Pd/PMe₃-catalyzed allylation of 1-(cyanomethyl)naphthalenes with allyl acetates proved to be para- rather than α-regioselective. This reaction is thought to proceed through ligand attack of the para-carbon in the arenes, electronically enriched by a cyano-stabilized α-carbanion, to the (π-allyl)palladium and a 1,5-hydrogen shift of the para-hydrogen from the dearomatized intermediate.