杂双金属复合物ZABDP催化芳香酮与芳香醛的直接不对称Aldol反应

摘要

合成了新型的手性铝/锌杂双金属复合物(R,S,S)-3,3′-二[(N-二苯基脯氨醇)甲基]-2,2′-二羟基- 1,1′-联萘酚铝/锌复合物(ZABDP).在催化芳香酮与芳香醛的羟醛缩合(Aldol)反应中, 该复合物中的铝作为路易斯酸活化醛, 锌的烷氧化物作为Br(o)nsted碱, 使苯乙酮形成活性锌的烯醇化物, 2种金属的应用使得芳香醛与芳香酮的直接不对称Aldol反应顺利进行, 反应的对映选择性最高达90%, 产率最高达99%.%A chiral Al/Zn heterobimetallic complex,(R,S,S)-3,3′-bis[(N-diphenylprolinol) methyl]-2,2′-bis-(methoxymethyl)-1,1′-binaphthol Al/Zn heterobimetallic complex(ZABDP) was designed as catalyst, to catalyze the direct asymmetric Aldol reaction of acetophenones and aromatic aldehydes.The Al center acts as a Lewis acid to activate the aldehydes while ethylzinc alkoxide functions as a Br(o)nsted base to form the reactive zinc enolates in the complex ZABDP.The distinct actors of the two different metals contribute to the efficient direct asymmetric Aldol reaction, the highest e.e.value is 90% and yield is 99%.