Theoretical Studies on the Mechanisms of Transfer Hydroformylation Between Hydrocinnamaldehyde and Norbornadiene Catalyzed by Rh(Xantphos)L Complexes†

doi:10.7503/cjcu20160489

Abstract

Abstract:

The mechanism of transfer hydroformylation reactions of hydrocinnamaldehyde with norbornadiene(nbd) catalyzed by the catalyst a[Rh(Xantphos)L] complex at M11-L/6-31G(d,p) was calculated(Pathway A). The α-C in the reactive aldehyde molecules actually bonds with one hydrogen atom at least to reduce the steric interaction between the aldehyde reactant and counterion section in C—H oxidative addition step. A little of alkane products observed experimentally, the mechanism of reactive course of decarbonylation of hydrocinnamaldehyde(Pathway B) was calculated. The theoretical study indicates that decarbonylation reaction is suppressed and the selectivity for dehydroformylation is calculated to be(styrene∶phenylethane>99∶1) with benzoate as counterion. The calculation results show that simple aldehyde propanal would prefer dehydroformylation reaction rather than decarbonylation reaction catalyzed by active catalyst a. Based on the reactive energy barrier profile, the hydroformylation of acceptor nbd accelerated the occurrence of dehydroformylation and made the whole transfer hydroformylation irreversible.

Key words: Transfer hydroformylation, Hydrocinnamaldehyde, Norbornadiene, Benzoate counterion, Density functional theory

CLC Number:

O641

TrendMD:

YANG Yongsheng, YANG Xin, TIAN Zhiyue, XUE Ying. Theoretical Studies on the Mechanisms of Transfer Hydroformylation Between Hydrocinnamaldehyde and Norbornadiene Catalyzed by Rh(Xantphos)L Complexes^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2199.

Figures/Tables 8

Fig.1 Transfer hydroformylation(A), sketch of the possible mechanisms for catalytic cycle of transfer hydroformylation reactions, proposed by Dong group(Pathway A)(B) and Pathway B for the reactive course of decarbonylation(C)

Fig.2 Optimized structure of active catalyst a

Fig.3 Free energy(kJ/mol) profile for the transfer hydroformylationSolid line(pathway A) is the hydroformylation reaction; the dotted line(pathway B) is the decarbonylation reaction.

Fig.4 Optimized geometry of TS-ab for oxidative addition of C—H bond with active catalyst aR1=Ph, R2=H; R1 and R2 can be equal to other groups.

Fig.5 Benzoate counterion coordinated at the equatorial site of b complex(A) and benzoate counterion coordinated at the axial site of b1 complex(B)

Fig.6 Optimized transition structures of β-H elimination step

Fig.7 Optimized transition structures of reductive elimination(A) and migratory extrusion of CO(B) with 3-methoxybenzoate as counterion

Fig.8 Free energy(kJ/mol) profile for the transfer hydroformylation of propanal with active catalyst aSolid line is the dehydroformylation reaction and the dotted line is the decarbonylation reaction.

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