Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones
Document Type
Article
Publication Date
1-1-2025
Abstract
We report a new method for the enantio- and diastereoselective synthesis of α-allene quaternary centers in fully substituted cyclohexanones at the α-positions. This reaction involves asymmetric 1,2-carbonyl addition to 2-O-propargyl enones using a mixture of Grignard reagents and the PMP-H8-BINOL ligand. The resulting magnesium alkoxide chelate intermediate then activated the propargyl vinyl ether moiety, thereby triggering a cascade propargyl Claisen rearrangement in a diastereoselective manner. The synthetic applications of this method in the context of complex molecules are also demonstrated.
Publication Source (Journal or Book title)
Organic Letters
Recommended Citation
Armendariz-Gonzalez, E., Saputra, A., Mureka, E., Locicero, C., Womble, G., Tan, G., Watson, A., Fronczek, F., & Kartika, R. (2025). Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones. Organic Letters https://doi.org/10.1021/acs.orglett.5c02006