Mechanistic insight into the diastereoselective rhodium-catalyzed Pauson-Khand reaction: role of coordination number in stereocontrol.
Mechanistic insight into the diastereoselective rhodium-catalyzed Pauson-Khand reaction: role of coordination number in stereocontrol.
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DOI：
10.1002/anie.200702822
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发表时间：
2008
影响因子：
--
通讯作者：
Huijun Wang;J. Sawyer;P. Evans;M. Baik
中科院分区：
文献类型：
--
作者：
Huijun Wang;J. Sawyer;P. Evans;M. Baik
Transition-metal-catalyzed higher-order [m + n + o] carbocyclization reactions represent powerful methods for the construction of complex polycyclic systems. [1] A key feature in these transformations is the dichotomy in reactivity that a substrate will display with different transition-metal complexes,reminiscent of enzyme-directed terpene biosynthesis. [2] Although catalyst-controlled reactions are very well established,they are generally identified empirically rather than through the ability to a priori select the optimal catalyst for a particular transformation. DFT calculations have emerged as a powerful predictive tool capable of aiding the design and understanding of these types of reactions and their application to challenging synthetic problems. [3] Herein,we demonstrate theoretically the impact of coordination number on the level of diastereocontrol in the rhodium-catalyzed Pauson–Khand (PK) reaction [Eq. (1)] and experimentally support the hypothesis. [4]
