Stereocontrolled synthesis of (E,Z)-dienals via tandem Rh(I)-catalyzed rearrangement of propargyl vinyl ethers. 2013

Dinesh V Vidhani, and Marie E Krafft, and Igor V Alabugin
Department of Chemistry & Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.

A novel Rh(I)-catalyzed approach to functionalized (E,Z) dienals has been developed via tandem transformation where a stereoselective hydrogen transfer follows a propargyl Claisen rearrangement. Z-Stereochemistry of the first double bond suggests the involvement of a six-membered cyclic intermediate whereas the E-stereochemistry of the second double bond stems from the subsequent protodemetalation step giving an (E,Z)-dienal.

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