Wei Han-Xun, Kim Sun Hee, Li Guigen
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA.
J Org Chem. 2002 Jul 12;67(14):4777-81. doi: 10.1021/jo0200769.
The FeCl(3)-PPh(3) complex was found to effectively catalyze the electrophilic diamination reaction of electron-deficient alkenes. Improvements on yields and stereoselectivity have been achieved for both alpha,beta-unsaturated carboxylic esters and ketones. Under the new catalytic system, alpha,beta-unsaturated carboxylic esters were found to be superior to their ketone counterparts, which is opposite to the previous (C(3)F(7)CO(2))(2)Rh](2)-catalyzed diamination. The reaction employs readily available N,N-dichloro-p-toluenesulfonamide (TsNCl(2)) and acetonitrile as the nitrogen sources and is very easy to perform at room temperature without the special protection of inert gases. The resulting diamino products belong to imidazolidine analogue and can further strengthen the importance of the new reaction. Modest to good yields (52-84%) and high regio- and stereoselectivity have been achieved for 10 examples.
发现FeCl(3)-PPh(3)络合物能有效催化缺电子烯烃的亲电双胺化反应。对于α,β-不饱和羧酸酯和酮，产率和立体选择性均有提高。在新的催化体系下，发现α,β-不饱和羧酸酯优于相应的酮，这与之前(C(3)F(7)CO(2))(2)Rh催化的双胺化反应相反。该反应使用易于获得的N,N-二氯对甲苯磺酰胺（TsNCl(2)）和乙腈作为氮源，在室温下无需惰性气体的特殊保护即可轻松进行。所得的二氨基产物属于咪唑烷类似物，这进一步增强了该新反应的重要性。10个实例的产率适中至良好（52 - 84%），区域选择性和立体选择性高。
