No abstract

Both dimeric μ-chlorine bridged and monomeric bidentate Pd(II) complexes with SCN hybrid pincer-type ligands, bearing thiophosphoryl group and imine moiety of the benzothiazole ring as coordination arms, formed in the reaction with (PhCN)(2)PdCl(2) under kinetic control (20 °C, dichloromethane solution) were readily converted into the corresponding SCN pincer complexes via solid phase synthesis (neat, 200 °C, 15 min). The synthesis of pincer complexes can be performed also by heating (200 °C, 5 min) of a homogeneous mixture of the initial reactants, namely, the ligand and (PhCN)(2)PdCl(2), obtained by manual grinding in a mortar. The efficacy of solid phase approaches is comparable with the analogous synthesis in solutions under severe conditions.

Macrobicycles derived from 1,8-disubstituted cyclam in principle may be planar-chiral provided that the second chain cannot rotate around the cyclam fragment. Hindered rotation is enabled by the introduction of two additional substituents at nitrogen atoms and by enough short chain which forms the second cycle. N,N',N",N'"-tetrasubstituted cam.ac.uk), deposit number CCDC 912600. Benzyl bromide, 3-bromobenzyl bromide, 2-(bromomethyl)naphthalene, 4-methylbiphenyl, propane-1,2-diamine, ethane-1,2-diamine, 1,2-diphenylethane-1,2-diamine, rac-BINAP, (R)-BINAP and other ferrocene-based chiral phosphine ligands, sodium tert-butoxide were purchased from Aldrich and Acros and used without further purification, Pd(dba) 2 was synthesized according to the method described.[22] 4-(Bromomethyl)biphenyl was synthesized from 4-methylbiphenyl by a standard procedure using NBS in CCl 4 with AIBN as radical initiator. Bis-formaldehide cyclam and 1,8-dibenzyl cyclam were provided by the CheMatech Co, Dijon, France. Dioxane was distilled over NaOH followed by the distillation over sodium under argon, dichloromethane and methanol were used freshly distilled.Typical procedure for the synthesis of 1,8-bis(arylmethyl) derivatives of cyclam 5, 6.In a one-neck flask (100 ml) bis-formaldehyde-cyclam (1) (2.50 g, 11.2 mmol) was dissolved in 52 ml CH 3 CN, corresponding bromomethyl substituted arene (2-(bromomethyl)naphthalene or 4-(bromomethyl)bipehenyl, 22.4 mmol) was added and the reaction mixture was stirred at room temperature for 72 h. The residue was filtered off, washed with CH 3 CN (3 ˟ 40 ml) and dried in vacuo to obtain di-salts 2 and 3. The deprotection was carried out as follows: di-salt (2 or 3, 5 mmol) was mixed with the aqueous solution of NaOH (8 g in 60 ml) and stirred at 80-90 o C for 48 h. The resulting compound (5 or 6) was taken with CH 2 Cl 2 , dried over anhydrous Na 2 SO 4 , the solvent was evaporated in vacuo to give pure product.1, 8

'-бинафталин-2,2'-диамина (БИНАМ) и N,N'-ди(3-бромфенил) замещенного оксадиамина и из N,N'-ди(3-бромфенил)

N,N'-bis(bromobenzyl) substituted diazacrown ethers were obtained in the reactions of corresponding free diazacrowns with two equivalents of bromobenzyl bromides in high yields. These compounds were introduced in the Pdcatalyzed amination reaction with 1,3-bis(aminomethyl) and 1,3-bis(2-aminoethyl)adamantanes to give macrobicyclic products. The yields were shown to be dependent on the nature of starting diazacrown derivatives and diamines. N,N'-bis(3-bromobenzyl)