Density functional studies on the Pauson--Khand reaction.
Density functional studies on the Pauson--Khand reaction.
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DOI：
10.1021/ja005565
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发表时间：
2001-01
影响因子：
15
通讯作者：
M. Yamanaka;E. Nakamura
中科院分区：
文献类型：
--
作者：
M. Yamanaka;E. Nakamura
Pauson—Khand反应是由Co(2)(Co)(8)催化的一步合成环戊酮的反应，通过[2 + 2 + 1]组装烯烃、炔和一氧化碳各一个分子。本文首次报道了Pauson—Khand （PK）反应途径的密度泛函研究（B3LYP/631LAN），为各种中间体和过渡态的结构和能量学提供了有价值的信息。PK反应包括烯烃插入、CO插入和还原消除三个步骤。发现烯烃插入步骤是一个不可逆的步骤，决定了整个反应的立体化学和区域化学。以下步骤为低活化能可逆过程。成键事件只发生在两个金属原子中的一个上，而第二个金属原子不仅作为锚点将金属团簇固定在有机底物上，而且对第一个原子的反应施加电子影响。
The Pauson--Khand reaction represents a one-step Co(2)(CO)(8)-catalyzed synthesis of cyclopentenone through [2 + 2 + 1] assembly of one molecule each of alkene, alkyne, and carbon monoxide. Density functional studies (B3LYP/631LAN) on the reaction pathway of the Pauson--Khand (PK) reaction reported here for the first time provides valuable information on the structures and energetics of various intermediates and transition states. The PK reaction consists of olefin insertion, CO insertion, and reductive elimination steps. The olefin insertion step was found to be an irreversible step that determines the stereo- and regiochemistry of the overall reaction. The following steps are low activation energy processes and reversible. The bond-forming events occur only on one of the two metal atoms, while the second metal atom not only acts as an anchor that fixes the metal cluster to the organic substrate but also exerts electronic influences on the reaction at the first atom.