Synthesis and reactivity of thiophene palladium and thiophene dipalladium complexes with unsaturated molecules

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

“…Thermodynamics also explain why the double insertion into M–C bonds, accomplishing M–CO–CO–C moieties, is not characteristic for carbon monoxide. On the contrary, the double or even multiple insertion giving M–(CNR) n –C oligomers and polymers is quite common for the isocyanide chemistry (Scheme ). ,,,− …”

“…Thienyl palladium 386 (Scheme ) and thienylene-bridged dipalladium 390 (Scheme ) complexes underwent insertion of one or more CNXyl molecules into their Pd–C bonds . Thus, treatment of 386 with 1 equiv of CNXyl furnished iminoacyl complexes 387 (CH 2 Cl 2 , RT, 16 h, 69–89%), and a 3-fold excess of CNXyl led to iminoacyl complexes 388 (CH 2 Cl 2 , RT, overnight, 74%).…”

Conversion of iminoacyl quinolinylpalladium (II) complexes into novel oxo‐pyrrolo[3,4‐b] quinolines via depalladation reactions

“…Oxidative addition reactions of 2-chloro-6-R-3-quinolinecraboxaldehydes [R = H (1a), R = OMe (1b)] with stoichiometric amounts of [Pd(dba) 2 ] = ([Pd 2 (dba) 3 ].dba; dba = dibenzylideneacetone) [53] in the neutral ligand such as PPh 3 (1 : 2 : 1) under nitrogen in degassed acetone giving the dimeric palladium complexes{Pd[C 9 H 5 -CHO(3)]Cl(PPh 3 )} 2 2a and {Pd[-6-OCH 3 -C 9 H 4 -CHO(3)]Cl(PPh 3 )} 2 2b in moderate yields (43 and 31%), through the coordination of quinolinyl nitrogen. Subsequently, the insertion reaction of 2,6-dimethylphenyl isocyanide XyNC (Xy = 2,6-Me 2 C 6 H 3 ) into dinuclear complexes in CH 2 Cl 2 at room temperature eventually formed monuclear complexes 3a, b in high yields (81 and 77%).…”

Synthesis of Novel Palladacycles Inhibitors of the Cathepsin B Activity and Antitumoral Agents

“…Based on the results described above, in the present paper, we investigated the interactions of cathepsin B with some palladacycles derived from the reaction of 2-Bromo-3,4,5-trimethoxybenzaldehyde 1 with [Pd 2 (dba) 3 ].dba (Pd(dba) 2 ; dba = dibenzylideneacetone), in the presence of N-donor ligands, such as N,N,N',N'-tetramethyl-ethane-1,2-diamine (TMEDA), (2,2'-bipyridine (bpy), (4,4'-dimethyl-2,2'-bipyridine (dmbpy) and 1,10-phenanthrroline (Phen). We concluded that the antitumor activity of the palladacycles compounds presented here can be attributed, at least in part, to the inhibitory properties of these complexes on the cysteine-protease activity, such as cathepsin B. Palladacycles are one of the most popular classes of organo palladium derivatives, which are widely applied in organic synthesis [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39], organometallic catalysis [40][41][42][43][44], and new molecular materials [24]. Among them, the most investigated cyclic Pd-complexes are five-or six-membered rings fused with an aromatic ring, and the metallated carbon is usually an aromatic sp2 carbon [35][36][37][38][39].…”