The isomerization of allylic alcohols has proved to be a very successful method for the synthesis of saturated carbonyl compounds. This reaction has been traditionally performed using transition-metal catalysts. In our group, we have recently reported that a very simple IrIII catalyst is able to isomerize primary and secondary allylic alcohols under very mild conditions. In the course of our investigations, we observed that electron-deficient allylic alcohols could be isomerized by base in the absence of a metal catalyst. Herein, we described a transition metal free isomerization of electron-deficient allylic alcohols and allylic ethers employing a very simple guanidine base, triazabicyclodecene (TBD). This method was found to be highly stereospecific and starting from enantiopure allylic alcohols and ethers, the corresponding chiral ketones and enol ethers were obtained with excellent ee. The scope of the reaction and experimental and computational mechanistic investigations will be presented.

Metal-free stereospecific isomerization of electron-deficient allylic alcohols and allylic ethers

254th National Meeting (2017)

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