Ortho vinylation of aromatic amides via cyclopalladation complexes

Anilide ortho‐Arylation by Using CH Activation Methodology

“…GC analyses were performed on a Shimadzu GC-2010 chromatograph equipped with a Restek column (Rtx-5, 15 m, 0.25 mm inner diameter). The 1 H and 13 C NMR spectra were recorded on a GE QE-300 spectrometer by using the residual solvent peak as a reference. IR spectra were obtained by using a ThermoNicolet Avatar 370 FT-IR instrument.…”

“…[12] As expected for an electrophilic CÀH activation process, the reactions are faster for anilides possessing donor substituents. [13] It has been shown that diaryliodonium trifluoromethanesulfonates can transfer Ar + to nitrogen-ligated Pd II , thereby leading to the formation of unstable Pd IV species that decompose through reductive elimination pathways. [14] This finding of Canty and co-workers may be relevant to the mechanism of this arylation procedure; however, at this point a s-bond metathesis pathway can not be ruled out.…”

Electrochemical Recycling of Benzoquinone in the Pd/Benzoquinone‐Catalyzed Heck‐Type Reactions from Arenes

“…The assumed intermediate dimeric complex 6 formed in the first step of the catalytic cycle, by activation of the Ar À H bond of 1, has indeed been isolated by Horino and Inoue and found to react with alkene (R = COMe) to give the arylated alkene. [7] One notices that the coordination of the Pd(II) center by the oxygen of the carbonyl group in complex 6 is sufficiently weak to allow the carbopalladation step to proceed. It has been indeed shown by Brown, Ricci et al that the formation of too stable palladacycles prevents the carbopalladation from proceeding.…”

Palladium-Catalyzed Group-Directed sp2-C—H Functionalization

“…(38) 值得一提的是, Chang [54] 和 Antonchick [55] 两个课题 组分别成功实现了乙酰苯胺类无金属催化的分子内 C-N 键的形成, 这个发现无疑是有机合成中杂环合成 的重大进步.…”