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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Palladium-catalyzed double-bond migration of unsaturated hydrocarbons accelerated by tantalum chloride
Masahito Murai1, Kengo Nishimura, Kazuhiko Takai
1Division of Applied Chemistry, Graduate School of Natural Science and Technology, and Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan. masahito.murai@okayama-u.ac.jp.
Abstract:
The operationally simple palladium-catalyzed double-bond migration without heteroatom-containing coordinating functional groups is described. Addition of TaCl5 as a second catalyst greatly enhanced the migration efficiency to provide β-alkylstyrenes through migration of up to a five-carbon chain. Both catalysts were commercially available, and the reaction occurred without external ligands under neutral conditions. The reaction proceeded via generation of π-allyl palladium species, which enabled the chemoselective double-bond migration of hydrocarbons in the presence of allylethers. Remote functionalization through double-bond migration was also demonstrated using FeCl3 as a second catalyst.
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