Organotin Reagents in Cross-Coupling Reactions

Belin Mart m-Matute, Kalman J. Szabo, and Terence N. Mitchell 

Cross-coupling reactions involving organotin derivatives are today linked indivisibly with the name of the late J. K. Stille, although it is known that he was not in fact the true inventor of this type of chemistry. 

In 2003, when the second edition appeared, it was clear that the Stille chemistr/ had really come of age, as shown by the increasing number of applications of palladium-catalyzed cross-coupling reactions of vinyl- and arylstannanes in natural product synthesis and in advanced organic synthesis. In the past decade, these types of applications, of course, remained very important and, in addition, the use of allylstannanes in palladium-catalyzed coupling reactions received much attention. Cross-coupling of allylstannanes with imines also forwarded the area of asymmetric catalysis. 

This chapter is divided according to a number of subject areas. First and foremost will come information on new catalyst systems that have served to increase the applicability of this chemistry. Second, some examples for the use of the Stille chemistry in natural product synthesis will be given this area is increasing explosively in importance. Applications in organic chemistry wiU then be presented, followed by selected examples dealing with the synthesis of polymeric and inorganic target molecules. 

Recent reviews that can be used to complement the presentation in this chapter ought to be mentioned [1-3]. Farina et al. [la] have done invaluable work in reviewing the Stille reaction, and the article (with 865 references ) published in 1997 in the series Organic Reactions was republished in 1998 in book form [lb]. The intramolecular variant of the reaction is of great importance, particularly for the preparation of macrocycles, and has been reviewed recently by Duncton and Pattenden [lc,d]. Applications of the Stille reaction in organometallic chemistry were reviewed by Lo Sterzo [2a,b]. Mechanisitic aspects have recently been discussed by Espinet and Echavarren [3a,b]. 

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Samuelsson, L. Langstrom, B. J. Labelled Comd. Radiopharm. 2003, 46, 263. MitcheU, T. N. Organotin Reagents in Cross-Coupling Reactions. In Metal-Catalyzed Cross-Coupling Reactions (2nd edn) De Meijere, A. Diederich, F. eds., 2004, 1, 125-161. WUey-VCH Weinheim, Germany. (Review). 

Mitchell TN (2004) Organotin Reagents in Cross-Coupling Reactions. In de Meijere A, Diederich F (eds) Metal-Catalyzed Cross-Coupling Reactions. Wiley, Wein-heim, p 125... 

Jeges G, Skoda-Eoldes R, Kollar L, Horvath J, Tuba Z (1998) Tetrahedron 54 6767 Skoda-Foldes R, Bodnar M, Kollar L, Horvath J, Tuba Z (1998) Steroids 63 93 Skoda-Eoldes R, Jeges G, Kollar L, Horvath J, Tuba Z (1996) Tetrahedron Lett 37 2085 Mitchell TN (2004) Organotin Reagents in Cross-Coupling Reactions. In de Meijere A, Diederich F (eds) Metal-Catalyzed Cross-Coupling Reactions. Wiley, Wein-heim, p 125... 

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