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Hydroformylation and Isomerization of Allene and Propyne: A Density Functional Theory Study
Author(s) -
Huo ChunFang,
Li YongWang,
Beller Matthias,
Jiao Haijun
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400725
Subject(s) - propyne , allene , hydroformylation , regioselectivity , isomerization , chemistry , density functional theory , nonanal , intramolecular force , allylic rearrangement , photochemistry , medicinal chemistry , computational chemistry , catalysis , stereochemistry , organic chemistry , rhodium
The [HCo(CO) 3 ]‐catalyzed hydroformylation of allene and propyne has been investigated at the B3LYP level of density functional theory. It is found that hydroformylation of allene favors the linear anti‐Markovnikov product in high regioselectivity both kinetically and thermodynamically. The origin of this regioselectivity comes from the enhanced stability of the η 3 ‐allylic intermediate [(η 3 ‐CH 2 CHCH 2 )Co(CO) 3 ]. By contrast, propyne does not show any regioselectivity. The possible interconversion between allene and propyne mediated by [HCo(CO) 3 ] has been explored.