Tuesday, May 20, 2008 - 9:10 AM
Medical Arts Building, Rm M-134 (Queensborough Community College)
376

Novel Approaches to the Cross-Coupling Reactions

Jing Liu1, Yingsheng Zhao2, Xiancai Luo2, and Aiwen Lei3. (1) Ms., Wuhan, China, (2) Mr., Wuhan, China, (3) Professor, Wuhan, China

 

During the past three decades, the bond formations (C-C, C-X)  promoted  by transition  metals  are  extensively  studied,  and  widely  applied  in  the organic syntheses as the most successful,  and reliable methods. In general, this transformation includes three elementary reactions: (1) oxidative addition, (2) Transmetallation, (3) Reductive Elimination.  Herein, we would like  to introduce a new approach: the oxidative cross-coupling, which involves double transmetallation, 1-3 and reductive elimination (Scheme 1).       Using desyl chloride as the oxidant, a Csp-Sn reagent and a Csp3-Zn reagent can couple together with surprisingly high selectivity.4 When the Csp3-Zn reagents have b-H, the coupling can take place well in high yield as well as the selectivity. The coupling of Csp-Sn and Csp2-Zn was also examined, and high yield of the desired cross-coupling products were obtained. Our kinetic data from ReactorIR, 13C NMR indicate that the organozinc reagents are highly oxophilic, and the organotin reagent might be halophilic.

References:

(1)  Lei, A.; Zhang, X. Tetrahedron Lett. 2002, 43, 2525-2528.

(2)  Lei, A.; Zhang, X. Org. Lett. 2002, 4, 2285-2288.

(3)  Lei, A.; Srivastava, M.; Zhang, X. J. Org. Chem. 2002, 67, 1969-1971.

(4)  Zhao, Y.; Wang, H.; Hou, X.; Hu, Y.; Lei, A.; Zhang, H.; Zhu, L. J. Am. Chem. Soc. 2006, 128, 15048-15049.