Publications [#148327] of Patrick Charbonneau

Papers Published

  1. Spivey, A. C. and Charbonneau, P. and Fekner, T. and Hochmuth, D. H. and Maddaford, A. and Malardier-Jugroot, C. and Redgrave, A. J. and Whitehead, M. A., "Energy barriers to rotation in axially chiral analogues of 4-(dimethylamino)pyridine", Journal of Organic Chemistry, 2001, 66(22), 7394-7401 [doi].
    (last updated on 2010/09/06)

    Abstract:
    The barriers to enantiomerization of a series of axially chiral biaryl analogues of 4-(dimethylamino)pyridine (DMAP) 1-10 were determined experimentally by means of dynamic HPLC measurements and racemization studies. The barriers to rotation in derivatives 1-6 (based on the bicyclic 5-azaindoline core) were lower than those in the corresponding derivatives 7-10 (based on the monocyclic DMAP core). Semiempirical (PM3), ab initio Hartree-Fock (HF/STO-3G), and density functional theory (DFT/B3LYP/6-31G*) calculations reveal that these differences in barriers to rotation are the result of differing degrees of hybridization of the non-pyridyl nitrogen in the enantiomerization transition states (TSs). The importance of heteroatom hybridization as a factor in determining nonsteric contributions to barriers to rotation in azabiaryls of this type is discussed.