American Chemical Society
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Regioselective Hydroformylation of Butadiene:  Density Functional Studies

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journal contribution
posted on 2005-07-18, 00:00 authored by Chun-Fang Huo, Yong-Wang Li, Matthias Beller, Haijun Jiao
The HCo(CO)3-catalyzed hydroformylation of butadiene has been investigated at the B3LYP density functional level of theory. It is found that butadiene hydroformylation favors the formal 1,4-addition product in high regioselectivity. The enhanced stability of the syn3-allyl complex ((η3-CH2CHCH(CH3))Co(CO)3) presents a distinctly thermodynamic preference for the Markovnikov insertion, and the following CO addition favors forming the 1,4-addition intermediate over the branched intermediate both kinetically and thermodynamically. Neither linear nor branched 1,2-addition product is favored. These results agree perfectly with the experimental findings. Furthermore, it is shown that methanol as solvent does not change the mechanistic picture significantly.