Kosugi-Stille Coupling

Similarly, the Migita-Kosugi-Stille cross-coupling reaction (Equation (115)) is important in organic synthesis and has IS 190 302 303, 1... 

STILLE CROSS-COUPLING (MIGITA-KOSUGI-STILLE COUPLING)... 

The first demonstration of palladium catalysis in an aryl amination reaction was reported in 1983 by Kosugi and co-workers. In this reaction, an aminostannane is coupled to an aryl halide in a transformation analogous to a Stille cross-coupling. 

Scheme 3-215. General catalytic cycle of Kosugi-Migita-Stille cross-coupling.

Cyclopentadienylstannanes can be used in the Migita-Kosugi-Stille reaction with organic iodides, RI, to give the cross-coupled product Cp-R, for example, Equation (117).310... 

Reaction with Organotin Reagents (Migita-Kosugi-Stille Coupling) 656... 

Tandem bromoallylations/ Stille couplings had been investigated previously. Kosugi, M. Sakaya, T. Ogawa, S. Migita, T. Bull. Chem. Soc. Jpn. 1993, 66, 3058-3061. 

Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 Cu-mediated reactions acetylenes, 10, 551 dienes, 10, 552... 

Cross-coupling reactions 5-alkenylboron boron compounds, 9, 208 with alkenylpalladium(II) complexes, 8, 280 5-alkylboron boron, 9, 206 in alkyne C-H activations, 10, 157 5-alkynylboron compounds, 9, 212 5-allylboron compounds, 9, 212 allystannanes, 3, 840 for aryl and alkenyl ethers via copper catalysts, 10, 650 via palladium catalysts, 10, 654 5-arylboron boron compounds, 9, 208 with bis(alkoxide)titanium alkyne complexes, 4, 276 carbonyls and imines, 11, 66 in catalytic C-F activation, 1, 737, 1, 748 for C-C bond formation Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 via Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 via Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 for C-H activation, 10, 116-117 for C-N bonds via amination, 10, 706 diborons, 9, 167... 

As organotin compounds (organostannanes) undergo smooth Pd-catalysed transmetallation, aryl halides react with a wide variety of aryl-, alkenyl- and alkylstannanes [139]. Coupling with allylstannane is the first example [140]. The reaction is called the Migita-Kosugi-Stille or Stille coupling. Aryl, alkenyl, allyl, alkynyl and benzyl... 

In 1994, Paul, Patt, and Hartwig showed that the Pd(0) catalyst in Kosugi s process was Pd[P(o-C6H4Me)312 (3), which underwent oxidative addition of aryl halides to give dimeric aryl halide complexes (4) [91]. These aryl halide complexes reacted directly with tin amides to form arylamine products (Eq. (3)). Thus, this chemistry could formally be viewed as being roughly parallel to Stille coupling. 

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