Palladium.docVIP

Palladium-Catalyzed Carbon?Carbon Coupling Reactions 2.1. Matsuda?Heck Reaction 2.1.1. Olefinic Coupling Partner Kikukawa and Matsuda were the pioneers in studying the reactivity of diazonium salts with transition metals. The new method emerged as a complementary strategy to the Meerwein reaction6 for the arylation of unactivated olefins and also as an improvement on the method proposed in the early studies with aryl halides that Mizoroki and Heck separately conducted.20 Kikukawa和Matsuda是研究重氮盐与过渡金属盐反应的先驱者。 The olefins that were arylated were styrene, cyclopentene, allylic alcohols, and ethyl acrylate. The in situ reduction of LiPd(II)Cl3 by sodium formate or Pd2(dba)3 as a source of Pd(0) in aqueous acetonitrile was used as a catalytic system. The reaction occurred at room temperature with sodium acetate as the base until production of nitrogen gas ceased. The same authors extended the methodology to the arylation of ethylene based on a comparative study of a variety of monosubstituted arenediazonium salts21,22 (Scheme 5). Some exceptions were oand p-nitrobenzenediazonium salts, which only gave nitrobenzene as the main reaction product. It seems that the reaction was also sensitive to the steric effects since mesitylenediazonium salt did not produce the corresponding styrene. A specific application by the same authors was vinylation of a benzocrown ether23 The detailed study of acrylonitrile was taken up again in 2001 when Cai et al.24 published a paper that investigated both the arylation of acrylonitrile and acrylamide with various arenediazonium tetrafluoroborates using Pd(OAc)2 in EtOH at 80 ?C. The corresponding (E)-cinnamonitrile and (E)-cinnamamide derivatives were obtained in yields of between 78% and 89%. In 2001, another paper published by Cai et al.25 reported yields of up to 63% for the arylation of alcohols 11 and 12 using Pd(OAc)2 as the catalyst in EtOH at 60 ?C. More recently, Muzart, Roglans et al.26 achieved the arylation of several allylic alcohol