Halides palladium-catalyzed coupling with alkenyl

Organozinc compounds are also useful in palladium-catalyzed coupling with aryl and alkenyl halides. Procedures for arylzinc,156 alkenylzinc,157 and alkylzinc158 reagents have been developed. The ferrocenyldiphosphine dppf has been found to be an especially good Pd ligand for these reactions.159... 

Tetrakis(triphenylphosphine)palladium catalyzes coupling of alkenyl halides with... 

Contrary to the general thought that palladium-catalyzed couplings of alkenyl halides are always stereoretentive the Suzuki-Miyaura coupling of (Z)-aIkenyl halides with boronic acids can give significant amounts of coupled products with ( )-configuration [78]. The best stereoretention was achieved with [Pd(P(o-Tol)3)2 as the catalyst. 

Most of the work on the C-N bond-forming crosscoupling reactions has concentrated on the formation of aromatic C-N bonds. Recent studies show that the application of cross-coupling reactions to alkenyl halides or triflates furnished enamines (Scheme 19) (for palladium-catalyzed reaction, see 28,28a-28d, and for copper-catalyzed reaction, see 28e-28g). Brookhart et al. studied the palladium-catalyzed amination of 2-triflatotropone 109 for the synthesis of 2-anilinotropone 110.28 It was found that the reaction of 109 proceeded effectively in the presence of racemic BINAP and a base. As a simple method for the synthesis of enamines, the palladium-catalyzed reactions of alkenyl bromide 111 with secondary amine were achieved under similar conditions.2841 The water-sensitive enamine 112 was isolated as pure compound after dilution with hexane and filtration through Celite. The intramolecular cyclization of /3-lactam 113, having a vinyl bromide moiety, was investigated by Mori s... 

The palladium-catalyzed coupling of boronic acids with aryl and alkenyl halides, the Suzuki reaction, is one of the most efficient C-C cross-coupling processes used in reactions on polymeric supports. These coupling reactions requires only gentle heating to 60-80 °C and the boronic acids used are nontoxic and stable towards air and water. The mild reaction conditions have made this reaction a powerful and widely used tool in the organic synthesis. When the Suzuki reaction is transferred to a solid support, the boronic add can be immobilized or used as a liquid reactant Carboni and Carreaux recently reported the preparation of the macroporous support that can be employed to efficiently immobilize and transform functionalized arylboronic adds (Scheme 3.12) [107, 246, 247]. 

Alkynyl(trimethyl)silanes smoothly couple with alkenyl halides at room temperature in the presence of a palladium catalyst and TASF (Eq. 5) [4]. The difference in reactivity between alkynylstannanes and -silanes were utilized in a palladium-catalyzed three component cross-coupling reaction. Thus, the palladium-catalyzed sequential reaction of tributylstannyl(trimethylsilyl)ethyne... 

Cross-coupling reactions have also been examined in water using amphiphilic PS-PEG resin-supported palladium complexes. Palladium-catalyzed coupling of aryl halides with aryl(or alkenyl)boronic acids (the so-called Suzuki-Miyaura coupling) took place in aqueous alkaline solution in the presence of polymeric catalyst 59 at 25 °C to give the biaryls in excellent yields [90,... 

The Negishi cross-coupling reaction is the nickel- or palladium-catalyzed coupling of organozinc compounds with various halides or triflates (aryl, alkenyl, alkynyl,... 

The Heck-Mizoroki reaction involves palladium-catalyzed coupling of an alkene with an alkenyl or aryl halide, leading to a substituted alkene. The alkene product is generally trans due to a 1,2-elimination step in the mechanism. 

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