Origin of the selectivity in directed ortho alumination of aromatic compounds mediated by TMP-aluminate

ORGN 635

Hiroshi Naka, naka@mail.pharm.tohoku.ac.jp1, James V. Morey2, Felipe García2, Hironaga Kudo1, Daisuke Nobuto3, Yoshinori Kondo1, Masanobu Uchiyama4, and Andrew E. H. Wheatley, aehw2@cam.ac.uk2. (1) Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Aoba-ku, Sendai 980-8578, Japan, (2) Department of Chemistry, Cambridge University, Lensfield Road, Cambridge, CB2 1EW, United Kingdom, (3) Graduate School of Pharmaceutical Sciences, The University of Tokyo, (4) Advanced Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
The experimental and theoretical study on the deprotonative metalation and post-metalation processes for TMP-aluminate (i-Bu3Al(TMP)Li, TMP = 2,2,6,6-tetramethylpiperidide) has been conducted, focusing on its reactivity towards N,N-dialkylbenzamides. Both DFT and X-ray crystallographic study revealed that the TMP-aluminate i) acts as an amido base but that, ii) unlike its zincate analogues it exhibits only a single-step directed ortho metalation. Further details including rationalization of this dichotomy will be presented in the session.

 

Materials, Devices and Switches, Metal-Mediated Reactions, Asymmetric Reactions, Total Synthesis, Biologically-Related Molecules and Processes
7:00 PM-9:00 PM, Wednesday, April 9, 2008 Morial Convention Center -- La Louisiane, Blrm. C, Poster

Division of Organic Chemistry

The 235th ACS National Meeting, New Orleans, LA, April 6-10, 2008