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

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.