Cross-coupling with organotin compounds

Arenediazonium and aryliodoitium salts are cross-coupled with organotin compounds in neat water or aqueous solvents (Scheme 55). The former can be used as prepared in... 

Zefirov s hypervalent iodine reagents were also used for cross-coupling with organotin compounds in aqueous systems. ... 

The cross-coupling of organotin compounds with aryl chlorides can be realized with either PCy3 (Pd(OAc)2/PCy3, K3P04, dioxane, reflux)402 or P Bu3 (Pd2dba3/P/Bu3, Pd L=l 2, CsF,... 

Dichloropyridine reacts in the dark (88% of disubstitution), whereas 2,6- and 3,5-dichloropyridines require photostimulation to afford ca. 80% yield of disubstitution products [26]. Aryltrialkylstannanes are valuable intermediates in organic synthesis, and the fact that they can be easily synthesized through the SRN1 mechanism, opens up important synthetic routes to different reaction schemes. For over a decade, the Pd(0)-catalyzed cross-coupling of organotin compounds with electrophiles, known as the Stille reaction, has been a very important tool in product design [104]. 

In the Stille cross-coupling, an organotin compound, such as a trimethylstannyl or tributylstannyl species, is coupled with an sp -hybridized halide in the presence of a catalytically active complex of Pd(0). The mechanism has been well... 

The cross-coupling reaction of alkenyl(fluoro)silanes with aryl halides sometimes produces, in addition to the desired ipso-cowpled products, small amounts of cmc-coupled products [14]. The czne-coupling is often striking in the reaction with organotin compounds. The isomer ratio of products produced by the reaction of l-fluoro(dimethyl)silyl-l-phenylethene with aryl iodides is found to depend on the electronic nature of a substituent on aryl iodides (Eq. 11) an electron-withdrawing group like trifluoromethyl and acetyl favors the formation of the ipso-coupled product. To explain the substituent effect, the mechanism depicted in Scheme 3 is proposed for the transmetalation of alkenylsilanes with palladium(ll) complexes. It is considered that an electron-donating substituent on Ar enhances... 

Hexamethyl- and Hexabutylditin. These ditins undergo cross-coupling with a variety of organohalides and pseudohalides (such as aryl halides, vinyl triflates, acyl chlorides, and allyl halides) in this protocol to give the correponding tin compounds. The reaction is particularly useful for preparation of organotins with labile functionalities that are not compatible with other procedures. 

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