86272-80-2

Upstream product

• 110-18-9 N,N,N,N,-tetramethylethylenediamine 
• 710316-98-6 1-(2-iodophenyl)-3-p-tolylurea 
• 533-58-4 2-Iodophenol 
• 868158-56-9 [Pd(C₆H₄NHC(O)NH(C₆H₄Me-4)-2)I(N,N,N',N'-tetramethylethylenediamine)] 
• 201230-82-2 carbon monoxide 
• 773887-40-4 [palladium(2-(OH)C₆H₄)I(N,N,N',N'-tetramethylethylenediamine)] 

Relevant academic research and scientific papers

Synthesis and reactivity of ortho-palladated arylureas. Synthesis and catalytic activity of a C,N,C pincer complex. Stoichiometric syntheses of some N-heterocycles

1-(2-Iodophenyl)-3-p-tolylurea (1) reacts with Pd(dba)2 ([Pd2(dba)3]·dba; dba = dibenzylide-neacetone) in the presence of the appropriate ligands to give the ortho-palladated arylureas [Pd{C6H4NHC(O)NHTo-2}IL2] (To = C 6H4Me-4; L2 = tbubpy (4,4′-di-tert-butyl- 2,2′-bipyridine) (2a), tmeda (N,N,N′,N′- tetramethylethylenediamine) (2b); L = PPh3 (2c)). Reaction of 2b with Tl(TfO) (TfO = triflate, CF3SO3) results in the formation of cyclopalladated [Pd{κ2C,O-C6H 4NHC(O)NHTo-2}(tmeda)]OTf (3b). The latter reacts with PPh 3 to yield [Pd{C6H4NHC-(O)NHTo-2}(tmeda) (PPh3)]OTf (4b). Treatment of 2b with CO gives the corresponding acyl derivative [Pd{C(O)C6H4NHC(O)NHTo-2}I(tmeda)] (5b). If Tl(TfO) is added after the bubbling of CO, the C,N coupling product 3-p-tolyl-1H-quinazoline-2,4-dione (6) is formed. Complex 5b reacts with XyNC (Xy = 2,6-dimethylphenyl) to yield trans-[Pd{C(O)C6H 4NHC-(O)NHTo-2}I(CNXy)2] (7). Both 5b and 7 decompose in solution to give 6. Complex 2b reacts with isocyanides to give the iminoacyl derivatives trans-[Pd{C(=NR)C6H4NHC(O)NHTo-2}I(CNR) 2] (R = Xy (8x), tBu (8t)). The complex 8x gives the C,N coupling product 4-(xylylimino)-3-p-tolyl-3,4-dihydro-1H-quinazolin-2-one (9) after treatment with TlOTf. 8x also reacts with bases (K2CO 3 and Tl2CO3) to yield the iminoacyl amido carbene C,N,C pincer palladium complex [Pd{κ3C,N,C-C(=NXy) C6H4NC(O)NToC(NHXy)-2}(CNXy)] (10); this complex is an active precatalyst in Heck and Suzuki reactions. The reaction of 2b with R′C≡ CR″ and TlOTf gives [Pd{κ2C,N-CR′= CR″C6H4NHC(O)NHTo-2}(tmeda)]OTf (R′ = R″ = Et (11be), CO2Me (11bm), Ph (11bp); R′ = Ph, R″ = CO2Me (11bq)). These complexes decompose in solution, and in the case of 11bp, 2,3-diphenylindole-1-carboxylic acid p-tolylamide (12p) was isolated, 11bq reacts with PPh3 to give 3-phenyl-1H-indole-2-carboxylic acid methyl ester (13q). 11bp and 11bq decompose in the presence of CO to yield 3,4-diphenyl-2-quinolone (14po) and 2-oxo-4-phenyl-l,2-dihydroquinoline-3- carboxylic acid methyl ester (14qo), respectively. Similarly, when 11bq is reacted with XyNC, the C,N coupling compound 2-xylyl-4-phenyl-1,2- dihydroquinoline-3-carboxylic acid methyl ester (14qnx) is formed. The crystal and molecular structures of 3b, 10·0.5CDCl3, 11bp·OEt2, 11bq, and 14po have been determined.

Reactivity of ortho-palladated phenol derivatives with unsaturated molecules. 1. Insertion of CO, isocyanides, alkenes, and alkynes. CO/alkene, alkyne/isocyanide, and isocyanide/alkene sequential insertion reactions

Ortho-palladated complexes of phenol derivatives were synthesized with unsaturated molecules. The insertion of alkenes into the palladium-carbon bond was found to be an important step in processes such as Heck reaction, polymerization of olefins and annulation of cyclic and bicyclic alkenes. It was observed that copolymerization of carbon monoxide (CO) and olefins using palladium catalysts takes place through alternating insertion of olefins and CO into the palladium carbon bond. The results show that the yields are better if the molar ratios of 2-iodophenol to Palladium and L2 to Palladium are 2/1 or even greater.