Manganese eta(2)-Complexes as Auxiliaries for Stereoselective Aldol Synthesis of Allenyl Carbinols

[摘要]：A convenient and robust manganese auxiliary was linked via an eta(2)-bond to alkynyl esters and ketones using a mild complexation reaction with methylcyclopentadienyl manganese tricarbonyl. This complex readily underwent aldol reactions with exclusive alpha-substitution and in good diastereoselectivities especially with aryl ketone substrates. This selectivity has been rationalized using a cyclic transition state model in which the manganese auxiliary plays a critical role in promoting E(O)-geometry of the cumulenolate intermediate.

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