Citation: Xiao-Jie Du, Yan-Hui Tang, Xin Zhang, Ming Lei. A theoretical study on the alkene insertion step in Rh-Yanphos catalyzed hydroformylation[J]. Chinese Chemical Letters, ;2013, 24(12): 1083-1086. shu

A theoretical study on the alkene insertion step in Rh-Yanphos catalyzed hydroformylation

1.
a State Key Laboratory of Chemical Resource Engineering, Institute of Materia Medica, College of Science, Beijing University of Chemical Technology, Beijing 100029, China;
2.
b College of Material Science and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China

Corresponding author: Ming Lei,
Received Date: 8 June 2013
Available Online: 19 June 2013
Fund Project:

This paper studied the mechanism of the alkene insertion elementary step in the asymmetric hydroformylation (AHF) catalyzed by RhH(CO)₂[(R,S)-Yanphos] using four alkene substrates (CH₂=CH- Ph, CH₂=CH-Ph-(p)-Me, CH₂=CH-C(=O)OCH₃ and CH₂=CH-OC(=O)-Ph, abbreviated as A1-A4). Interestingly, the equatorial vertical coordination mode (A mode) with respect to the Rh center was found for A1 and A2 but not for A3 and A4, although the equatorial in-plane coordinationmode (Emode) was found for A1-A4. The relative energy of the Emode of the η²-intermediates is lower than that of the A mode. In the alkene insertion step, Path 1 is more favorable than Path 2 for this system. As for A1 and A2, there could be a transformation between 2_eq and 2_ax.
- DFT,
- Hydroformylation,
- Mechanism,
- Alkene insertion,
- Coordination mode
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沈阳化工大学材料科学与工程学院沈阳 110142