TY - JOUR
T1 - Nature of intermediates in organo-somo catalysis of α-arylation of aldehydes
AU - Um, Joann M.
AU - Gutierrez, Osvaldo
AU - Schoenebeck, Franziska
AU - Houk, K. N.
AU - Macmillan, David W.C.
PY - 2010/5/5
Y1 - 2010/5/5
N2 - The intramolecular α-arylation of aldehydes via organo-SOMO catalysis was investigated using density functional theory (B3LYP and M06-2X functionals). The geometries, spin densities, Mulliken charges, and molecular orbitals of the reacting enamine radical cations were analyzed, and the nature of the resulting cyclized radical cation intermediates was characterized. In agreement with experimental observations, the calculated 1,3-disubstituted aromatic system shows ortho selectivity, while the 1,3,4-trisubstituted systems show para, meta (instead of ortho, meta) selectivity. The selectivity change for the trisubstituted rings is attributed to a distortion of the ortho substituents in the ortho, meta cyclization transition structures that causes a destabilization of these isomers and therefore results in selectivity for the para, meta product.
AB - The intramolecular α-arylation of aldehydes via organo-SOMO catalysis was investigated using density functional theory (B3LYP and M06-2X functionals). The geometries, spin densities, Mulliken charges, and molecular orbitals of the reacting enamine radical cations were analyzed, and the nature of the resulting cyclized radical cation intermediates was characterized. In agreement with experimental observations, the calculated 1,3-disubstituted aromatic system shows ortho selectivity, while the 1,3,4-trisubstituted systems show para, meta (instead of ortho, meta) selectivity. The selectivity change for the trisubstituted rings is attributed to a distortion of the ortho substituents in the ortho, meta cyclization transition structures that causes a destabilization of these isomers and therefore results in selectivity for the para, meta product.
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U2 - 10.1021/ja9063074
DO - 10.1021/ja9063074
M3 - Article
C2 - 20387888
AN - SCOPUS:77951688144
SN - 0002-7863
VL - 132
SP - 6001
EP - 6005
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 17
ER -