New usages for diphenyliodonium salts: Latent precursors of phenyl cation, anion, radical, and benzyne

ORGN 173

Terutaka Hatano, ff56024@mail.ecc.u-tokyo.ac.jp1, Masanobu Uchiyama1, Hiroyuki Kagechika, kage.omc@tmd.ac.jp2, Akiko Mine3, and Takao Sakamoto3. (1) Graduate School of Pharmaceutical Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan, (2) School of Biomedical Science, Tokyo Medical and Dental University, 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo, 101-0062, Japan, (3) Graduate School of Science, Tohoku University, Aobayama, Aoba-ku, Sendai
We investigated systematically the halogen-metal exchange reaction, deprotonative benzyne formation, and reductive ligand coupling of the aryliodonium salts through control of the reaction sites in the aryliodonium salts by using various metal reagents. Only ate complexes turned out to be effective for the accomplishment of these reactions. Tuning of the complexation environment of ate complexes was crucial for these transformations. For instance, the reaction of diphenyliodonium salts with n-Bu3ZnLi (or RLi) gave butylbenzene as the sole product, while the iodine-zinc exchange reaction and deprotonative benzyne formation proceeded selectively with Me3ZnLi and Me2Zn(TMP)Li, respectively. On the other hand, in the reaction of diphenyliodonium salts using Me3MnLi, single-electron reductive ligand coupling reaction proceeded to give biphenyl in high yield. Therefore, this work expands the possible usages of diaryliodonium salts, which could be available as aryl anions, benzynes, and aryl radicals.
 

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