A DFT study on hetero-Diels-Alder reactions catalyzed by cobalt complexes: Lewis acidity enhancement as a consequence of spin transition caused by Lewis base coordination.
A DFT study on hetero-Diels-Alder reactions catalyzed by cobalt complexes: Lewis acidity enhancement as a consequence of spin transition caused by Lewis base coordination.
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DOI：
10.1002/anie.200460836
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发表时间：
2005-04
影响因子：
--
通讯作者：
I. Iwakura;T. Ikeno*;T. Yamada
中科院分区：
文献类型：
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作者：
I. Iwakura;T. Ikeno*;T. Yamada
（给出的化学方程式）对 3-氧代亚丁基氨基钴 (II) 和钴 (III) 配合物催化的杂狄尔斯-阿尔德反应的密度泛函计算表明，醛作为路易斯碱的轴向配位会在 Co III 催化循环中诱导自旋跃迁。配合物的路易斯酸性增加，Co-O醛距离缩短（见图；Co绿，N蓝，O红），对映选择性提高。
(Chemical Equation Presented) Density functional calculations on the hetero-Diels-Alder reaction catalyzed by 3-oxobutylideneaminatocobalt (II) and-cobalt (III) complexes revealed that axial coordination of an aldehyde as a Lewis base induces a spin transition in the Co III catalytic cycle. The Lewis acidity of the complex is increased, the Co-O aldehyde distance shortened (see picture; Co green, N blue, O red), and the enantioselectivity improved.