Copper complexes diamine

Kanemasa et al. (60) showed that chiral diamine-copper complexes are moderately effective catalysts for cyclopropanation. Phenylhydrazine reduction of the complex formed from Cu(OTf)2 and excess diamine afforded the active catalyst. Cyclopropanation of styrene proceeds in moderate diastereoselectivity and good enantioselectivity with these catalysts, Eq. 43. 

The basic study was performed on copper complexes with N,N,N, N1-tetramethylethane-1,2-diamine (TMED), which were known to be very effective oxidative coupling catalysts (7,12). From our first kinetic studies it appeared that binuclear copper complexes are the active species as in some copper-containing enzymes. By applying the very strongly chelating TMED we were able to isolate crystals of the catalyst and to determine its structure by X-ray diffraction (13). Figure 1 shows this structure for the TMED complex of basic copper chloride Cu(0H)Cl prepared from CuCl by oxidation in moist pyridine. 

Kx for copper (II)-diamine complex is 10.36 and 9.45 for 1,2-ethanediamine and 1,3-propanediamine, respectively (-2)]. The large difference in the stabilities of the two copper (II)-diamine complexes is attributed to an unfavorable entropy effect associated with an increase in the size of the metal-chelate ring (2). Extrapolating to the / -ketoimine derivatives, it seems reasonable to expect that the stability of bisacetylacetonetrimethylenediiminocopper(II) would be less than that of the ethylenediamine analog and to suspect that the former compound is less stable than bis-(4-iminopentane-2-ono) copper (II). That this is reasonable is... 

Drury III, L. Ryzhkov, A. E. Taggi, T. Lectka, J. Am. Chem. Soc. 2002, 124, 67 for an example using chiral copper complexes derived either from xylyl-BINAP or chiral diamines, see i) S. Kobayashi,... 

Nakajima and co-workers have carried out extensive investigations into the influence of different chiral diamine-copper complexes on the oxidative dimerization of naphthols [146-148]. As emerged from Smrcina s work, the inclusion of an ester moiety on the naphthol precursor is an important factor for optimizing the enantioselectivity. After establishing a catalytic cycle with TMDA as the base and showing that sparteine gave promising results (Scheme 57), they focused their work on other chiral diamines (Table 39) [147]. 

The copper complex of the diaminodiol (98) functions as a model foT galactose oxidase.A related diamidodiol (99) has been reported binding to high-valent Os and Ru, as well as in mixed [Cu L M(bipy)2] (M = Co, Ni, Zn) compounds, some of the latter being antiferromagnetically coupled. A number of diamine-diacid ligands have appeared, such as (100), ... 

Collman, J. P., Zhong, M. An Efficient Diamine-Copper Complex-Catalyzed Coupling of Arylboronic Acids with Imidazoles. Org. Lett. 2000, 2,1233-1236. 

Komeen . [Griffin] Copper-ethylene-diamine complex aquatic herbicide for golf courses, fish ponds, potable water reservoirs. 

The most effective catalysts were found to be the 1 1 copper complexes with a,a -dipyridyl, L-histidine, o-phenanthroline, imidazole, and ethylene-diamine. Because of the apparent requirement that the metal be incompletely coordinated, it was suggested that the reactive positions of the metal are those occupied by water or hydroxide ion. Three such species have been reported by Fowkes et al. (9) from a study of aqueous equilibria involving the 1 1 dipyridyl chelate, according to the following reaction scheme ... 

PREPARATIVE TECHNIQUES Prepared by oxidative C-O coupling polymerization of 2,6-dimethylphenol in an aromatic solvent at room temperature in the presence of a catalyst. Generally, the catalyst is a copper and diamine complex. 

C6.C12) Alkyl carboxylic acid, trimethylolpropane triester. See Trimethylolpropane tricaprylate/tricaprate (C10-C18) alkylsulfonic acid, sodium salt. See Sodium C10-18 alkyl sulfonate C29-70 carboxylic acids. See C29-70 acid CCA Type C Wood Preservative 50-60%. See Chromate copper arsenate CCC. See Chlormequat chloride Calcium cyanamide Chlorophyllin-copper complex N-(C14-C18) and (C18-C18) unsaturated alkylpropylenediamine C14-C18 and C18-18-unsat. N-(alkyl) propylene diamine. See Tallowaminopropylamine (C18-C18) and (Cl 8) unsaturated alkylcarboxylic acid. See Palmitic/oleic acids (C18-C18) and C18 unsaturated alkyidimethylamine. See Dimethyl oleic-linolenic amine... 

Synonyms Cupriethylene diamine Cupriethylenediamine solution 1,2-Diaminoethane copper complex Ethane, 1,2-diamino-, copper complex Empirical C2H10N2 xCu Properties M.w. 506.92 Toxicology LD50 (oral, rat) 750 mg/kg, (skin, rabbit) > 8 g/kg corrosive poison irritating and corrosive to skin, eyes, and mucous membranes... 

The oxidation of substituted o-diphenols to the corresponding o-benzoquinones in the presence of 4 different binuclear copper complexes has been investigated by Bolus and Vigee [14]. The initial rates of oxidation were within a factor of 4 for the substrates catechol, 4-methylcatechol, dopamine, 3,4-dihydroxybenzoic acid, and 3,4-dihydroxybenzonitrile. The ligands of the catalyst complexes were Schiff-base type derivatives of 2,6-diformyI-4-methylphenol with diamines and amino acids their synthesis and characterization have been reported [15]. 

---