Promotion of Asymmetric Aza-Claisen Rearrangement of N-Allylic Carboxamides Using Excess Base

[摘要]：The aza-Claisen rearrangement of the enolate of N-(Z)-crotyl- N-(S)-phenethylpropanamide did not proceed in the presence of 1.5 equivalents of LHMDS as a base. However, the use of a large excess of base (10 equiv) promoted the reaction to give N-(S)-phenethyl- anti-2,3-dimethylpent-4-enamide with good stereoselectivities (anti/syn = ca. 95:5). An excess of base stabilized the amide enolates and prevented the decomposition to the ketene to prompt the rearrangement of various carboxamides with good stereoselectivity. This reaction provided a new method for the construction of asymmetric quaternary carbon centers.

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