Synthesis 2017; 49(16): 3569-3575
DOI: 10.1055/s-0036-1588842
special topic
© Georg Thieme Verlag Stuttgart · New York

Nickel-Catalyzed Hydroalkenylation of Alkynes through C–F Bond Activation: Synthesis of 2-Fluoro-1,3-dienes

Yota Watabe
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan   Email: junji@chem.tsukuba.ac.jp
,
Kohei Kanazawa
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan   Email: junji@chem.tsukuba.ac.jp
,
Takeshi Fujita
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan   Email: junji@chem.tsukuba.ac.jp
,
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan   Email: junji@chem.tsukuba.ac.jp
› Author Affiliations
This work was financially supported by JSPS KAKENHI Grant No. JP16H01002 (J.I.) for Precisely Designed Catalysts with Customized Scaffolding, and JSPS KAKENHI Grant No. JP16K20939 (T.F.) for a Grant-in-Aid for Young Scientists (B). We acknowledge Kanto Denka Kogyo Co., Ltd., for a generous gift of ethyl bromodifluoroacetate.
Further Information

Publication History

Received: 24 March 2017

Accepted after revision: 02 May 2017

Publication Date:
12 June 2017 (online)


Published as part of the Special Topic Advanced Strategies in Synthesis with Nickel

Abstract

2-Fluoro-1,3-dienes were synthesized through nickel-catalyzed coupling reactions between β,β-difluorostyrenes and alkynes in the presence of ZrF4 as co-catalyst and a hydride source derived from triethylborane and lithium isopropoxide. Mechanistic studies revealed that the carbon–fluorine bond was cleaved by β-fluorine elimination from intermediary nickelacyclopentenes generated through oxidative cyclization of the two substrates.

Supporting Information