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Soft Propargylic Deprotonation: Designed Ligand Enables Au-Catalyzed Isomerization of Alkynes to 1,3-Dienes

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journal contribution
posted on 17.12.2015, 02:53 by Zhixun Wang, Yanzhao Wang, Liming Zhang
By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold­(I) complex possesses orthogonally positioned “push” and “pull” forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pKa units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.