Synlett
DOI: 10.1055/s-0036-1590914
letter
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Allylation of Polyfluoroarenes with Allylic Pivalates

Xinpeng Jianga, Yong Liua, Lei Zhanga, Jinkang Chena, Kang Chenga, Chuanming Yu*a, b
  • aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
  • bCollaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   Email: ycm@zjut.edu.cn
This work was supported by the National Natural Science Foundation of China (NSFC) (grants numbers 21676252 and 21506191).
Further Information

Publication History

Received: 04 July 2017

Accepted after revision: 03 September 2017

Publication Date:
19 September 2017 (eFirst)

Abstract

An efficient 1,5-cyclooctadiene–PdCl2/dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (XPhos) catalytic system was developed for C–H allylation of polyfluoroarenes with allylic pivalates. The reactions showed excellent functional-group tolerance, good yields, and high regioselectivities. Mechanistic investigations supported a (π-allyl)palladium complex pathway through a directed oxidative addition of the allylic pivalate to palladium, followed by sequential nucleophilic attack by the polyfluorobenzene and reductive elimination. In a gram-scale reaction, a palladium loading of 0.5 mol% was enough to afford the required product in good yield.

Supporting Information