Structure, reaction pathway, and origin of selectivity of TMP-Zn-ates, R2Zn(TMP)Li

ORGN 176

Daisuke Nobutou1, Yotaro Matsumoto1, Masanobu Uchiyama, uchiyama@mol.f.u-tokyo.ac.jp1, and Keiji Morokuma, morokuma@emory.edu2. (1) Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, (2) Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA 30322
We present the first comprehensive structural and mechanistic investigation by means of X-ray, NMR, and DFT studies on the directed ortho metalation reactions employing our original TMP-Zn-ate bases, R2Zn(TMP)Li (R = Me or tBu). The structures of the TMP-Zn-ates in solution and in the solid state were determined. The DFT study strongly suggested that the deprotonation involving the TMP ligand on the TMP-Zn-ate was kinetically more favorable than that involving the alkyl ligand when anisole was used as a model substrate, and this view was supported by monitoring of the 13C-NMR spectrum of the reaction mixture.
 

Asymmetric Reactions and Syntheses, Metal-Mediated Reactions, Combinatorial, Parallel, and Solid-Phase Chemistry
8:00 PM-10:00 PM, Sunday, 10 September 2006 Moscone Center -- Hall D, Poster

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006