I  U  P  A  C




News & Notices

Organizations & People

Standing Committees




. . CI
. . PAC
. . Macro. Symp.

. . Books
. . Solubility Data



Links of Interest

Search the Site

Home Page


Pure Appl. Chem. Vol. 74, No. 1, pp. 143-149 (2002)

Pure and Applied Chemistry

Vol. 74, Issue 1

Metal-assisted amination with oxime derivatives*

Koichi Narasaka

Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

Abstract: Electrophilic amination of Grignard reagents is accomplished by using O-sulfonyl-oximes of benzophenone derivatives. In the presence of a catalytic amount of CuCN, O-sulfonyloxime of 4,4¢-bis(trifluoromethyl)benzophenone reacts with alkyl Grignard reagents in tetrahydrofuran (THF) and hexamethylphosphoramide (HMPA), yielding primary alkyl-amines by successive hydrolysis of the resulting N-alkylimines. Arylamines are also prepared as well as alkylamines by treating O-sulfonyloxime of 3,3¢,5,5¢-tetrakis(trifluoromethyl)benzophenone in toluene-ether with Grignard reagents.

Various cyclic imines are synthesized by palladium-catalyzed cyclization of olefinic oxime derivatives. That is, the reaction of O-pentafluorobenzoyloximes of olefinic ketones with a catalytic amount of Pd(PPh3)4 and triethylamine in dimethylformamide (DMF) affords nitrogen-containing heterocycles, such as pyrroles, pyridines, isoquinolines, spiro-imines, and aza-azulenes. This reaction proceeds via the initial formation of alkylideneaminopalladium species generated by oxidative addition of oximes to Pd(0), and the successive intramolecular Heck-type amination occurs on the olefinic moiety.

*Lecture presented at the 11th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-11), Taipei, Taiwan, 22-26 July 2001. Other presentations are presented in this issue, pp.1-186.
**Corresponding author.


Page last modified 21 March 2002.
Copyright © 2002 International Union of Pure and Applied Chemistry.
Questions or comments about IUPAC, please contact, the Secretariat.
Questions regarding the website, please contact web manager.