Nature of intermediates in organo-SOMO catalysis of alpha-arylation of aldehydes. Academic Article

abstract

• The intramolecular alpha-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.

authors

• Gutierrez Santacruz, Osvaldo

published proceedings

• J Am Chem Soc

author list (cited authors)

• Um, J. M., Gutierrez, O., Schoenebeck, F., Houk, K. N., & MacMillan, D.

citation count

• 117

complete list of authors

• Um, Joann M||Gutierrez, Osvaldo||Schoenebeck, Franziska||Houk, KN||MacMillan, David WC

publication date

• January 2010

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• Aldehydes
• Catalysis
• Cyclization

PubMed Central ID

• 20387888

Digital Object Identifier (DOI)

• 10.1021/ja9063074

start page

• 6001

end page

• 6005

volume

• 132

issue

• 17

URL

• http://dx.doi.org/10.1021/ja9063074