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Updated: Jul 2, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Silyl-Group Boosted Internal Redox Reaction: Hydride Shift from an Aliphatic Secondary Position for the Formation of
Hiroto Okawa1, Tomoko Kawasaki-Takasuka1, Keiji Mori1
1Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan.
Abstract:
We report a hydride shift/cyclization reaction at the aliphatic secondary position (methylene group). The key to accomplishing this reaction was the employment of benzylidene malonate having a silyl group β to the hydride donor carbon. When the corresponding malonates were treated with a catalytic amount of Al(OTf)3, the [1,5]-hydride shift from the simple aliphatic secondary position proceeded smoothly to afford silyl-group substituted tetralin derivatives in excellent chemical yields (up to 98%). This reaction system was applied to the formation of seven-membered carbocycles via the [1,6]-hydride shift mediated process.
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