Carbon–hydrogen and C–X (X = Cl or SiMe₃) bond activation. 1-Cyclopalladation and oxidation of some derivatives of 2-[(dimethylamino)methyl]naphthalene

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

“…The direct palladation route is not regioselective in the case of NCN-pincer ligands as both ortho-ortho and ortho-para palladation takes place [34]. Here, the use of an ortho-ortho directing group such as a trimethylsilyl one allows regioselective bis-(ortho)-palladation (Scheme 3) [35].…”

Selective intramolecular cleavage of the carbon-silicon bond by palladium salts

“…The chemoselectivity of the silicon-directed palladation may be different from that of direct palladation; 3-methyl-2-[(dimethylamino)methyl]naphthalene selectively reacts with palladium salts to give the l-palladated product (i.e. aromatic palladation) [7], but its trimethylsilyl substituted derivate 5 undergoes benzylic palladation only.…”

“…However, in our experience, the overall yield of the reaction of the organolithium species with Me,SiCl, followed by reaction with a palladium salt is better, and the silicon-directed cyclopalladations are faster than the corresponding reactions involving C-H cleavage. [7] and the complexes la, Za, 5a and 6a [HI were prepared as described previously. 'H-and 13C-spectra were recorded on a Bruker AC-200 MHz or a AC-300 spectrometer.…”

“…The yields obtained in both procedures are given in Table 1. (The reaction of the 3-naphthyl substrate 1 is included for the sake of completeness, although it was reported previously [7]). …”

Reactions of m-chloroperoxybenzoic acid with dimeric cyclopalladated complexes derived from 2-phenyl-2-oxazolines

“…Oxygen insertion into the C-Pd bond of cyclopalladated complexes can be accomplished by any of the following reagents: m-chloroperoxybenzoic acid (m-CPBA) (used alone [34][35][36][37][38][39][40][41][42][43][44][45][46] or with an iron(III) porphyrin catalyst [37]), other peroxy acids [40], t-BuOOH (used alone [47][48][49][50] or with a catalyst [34,35,[47][48][49][50][51][52]), hydrogen peroxide in the presence of an iron(III) porphyrin catalyst [53], pentafluoroiodosylbenzene C 6 F 5 IO (alone [37,52], in a combination with t-BuOOH [37,52] or in the presence of an iron(III) porphyrin catalyst [37,52]), iodosylbenzene C 6 H 5 IO [54], [di(benzoyloxy)iodo]benzene PhI(O 2 CPh) 2 [55] and the molybdenum peroxide MoO(O 2 ) 2 ÁHMPAÁH 2 O (HMPA = hexamethylphosphoric triamide) [14,56]. The mechanisms involved in these transformations appear to be different [5]; however, in all cases, the C-Pd bond is transformed into the C-O-Pd moiety.…”