Synfacts 2009(2): 0221-0221  
DOI: 10.1055/s-0028-1087617
Polymer-Supported Synthesis
© Georg Thieme Verlag Stuttgart ˙ New York

Clean Stille Reaction with Recyclable Stannylated Polynorbornenes

Contributor(s): Yasuhiro Uozumi, Yoichi M. A. Yamada, Hidetoshi Ohta
N. Carrera, E. Gutiérrez, R. Benavente, M. M. Villavieja, A. C. Albéniz*, P. Espinet*
Universidad de Valladolid, Spain
Further Information

Publication History

Publication Date:
22 January 2009 (online)

Significance

The organostannylated polynorbornenes 3-7 were prepared with a view toward using them in the Stille reaction. Thus, the radical hydrostannylation of norbornadiene with in situ generated HSnBu2Cl gave the chlorostannylated norbornenes 1 as a mixture of isomers. The vinylic copolymerization of 1 with norbornene (NB) catalyzed by [Ni(C6F5)2(SbPh3)2] gave 1/NB copolymer 2 in 66% yield. Then, the reaction of 2 with Grignard or organolithium reagents afforded 3-7 in 70-80% yield. The Stille reaction of 3-7 with 8-11 was carried out in the presence of a palladium catalyst to give the polymeric tin coproduct 12 and the corresponding coupling products 13 (64-100% yield).