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

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 equator...

Full description

Saved in:
Bibliographic Details
Published in:Chinese chemical letters 2013-12, Vol.24 (12), p.1083-1086
Main Authors: Du, Xiao-Jie, Tang, Yan-Hui, Zhang, Xin, Lei, Ming
Format: Article
Language:English
Subjects:
AHF
Alkene insertion
Coordination mode
DFT
Hydroformylation
Mechanism
中间体
催化羰基化
加氢甲酰化
烯烃
相对能量
铑
非对称
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 AI and A2 but not for A3 and A4, although the equatorial in-plane coordination mode （E mode） was found for A1 -A4. The relative energy of the E mode of the -q2-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 AI and A2, there could be a transformation between 2eq and 2ax.
ISSN:1001-8417
1878-5964
DOI:10.1016/j.cclet.2013.07.004