New benzo[h]quinoline-based ligands and their pincer Ru and Os complexes for efficient catalytic transfer hydrogenation of carbonyl compounds

New benzo[h]quinoline ligands (HCN'N) containing a CHRNH2 (R=H (a), Me (b), tBu (c)) function in the 2-position were prepared starting from benzo[h]quinoline N-oxide (in the case of ligand a) and 2-chlorobenzo[h]quinoline (for ligands b and c). These compounds were used to prepare ruthenium and osmium complexes, which are excellent catalysts for the transfer hydrogenation (TH) of ketones. The reaction of a with [RuCl2(PPh3)3] in 2-propanol at reflux afforded the terdentate CN'N complex [RuCl(CN'N)(PPh3)2] (1), whereas the complexes [RuCl(CN'N)(dppb)] (2-4; dppb=Ph2P(CH2)4PPh2) were obtained from [RuCl2(PPh3)(dppb)] with a-c, respectively. Employment of (R,S)-Josiphos, (S,R)-Josiphos*, (S,S)-Skewphos, and (S)-MeO-Biphep in combination with [RuCl2(PPh3)3] and ligand a gave the chiral derivatives [RuCl(CN'N)(PP)] (5-8). The osmium complex [OsCl(CN'N)(dppb)] (12) was prepared by treatment of [OsCl2(PPh3)3] with dppb and ligand a. Reaction of the chloride 2 and 12 with NaOiPr in 2-propanol/toluene afforded the hydride complexes [MH(CN'N)(dppb)] (M=Ru 10, Os 14), through elimination of acetone from [M(OiPr)(CN'N)(dppb)] (M=Ru 9, Os 13). The species 9 and 13 easily reacted with 4,4'-difluorobenzophenone, via 10 and 14, respectively, affording the corresponding isolable alkoxides [M(OR)(CN'N)(dppb)] (M=Ru 11, Os 15). The complexes [MX(CN'N)(P2)] (1-15) (M=Ru, Os; X=Cl, H, OR; P=PPh3 and P2=diphosphane) are efficient catalysts for the TH of carbonyl compounds with 2-propanol in the presence of NaOiPr (2 mol %). Turnover frequency (TOF) values up to 1.8x10(6) h(-1) have been achieved using 0.02-0.001 mol % of catalyst. Much the same activity has been observed for the Ru--Cl, --H, --OR, and the Os--Cl derivatives, whereas the Os--H and Os--OR derivatives display significantly lower activity on account of their high oxygen sensitivity. The chiral Ru complexes 5-8 catalyze the asymmetric TH of methyl-aryl ketones with TOF approximately 10(5) h(-1) at 60 degrees C, up to 97 % enatiomeric excess (ee) and remarkably high productivity (0.005 mol % catalyst loading). High catalytic activity (TOF up to 2.2x10(5) h(-1)) and enantioselectivity (up to 98 % ee) have also been achieved with the in-situ-generated catalysts prepared from [MCl2(PPh3)3], (S,R)-Josiphos or (S,R)-Josiphos*, and the benzo[h]quinoline ligands a-c.     

Convenient diastereospecific synthesis of a rociverine precursor and its resolution by lipase-catalyzed transesterification

(±)-1-Cyclohexyl-c-2-hydroxymethyl-r-1-cyclohexanol 3, a precursor of the antimuscarinic drug Rociverine 1, was obtained diastereospecifically in very high yield, from the Grignard reaction between C₆H₁₁MgCl and an appropriately protected 2-(hydroxymethyl)cyclohexanone. The preparation of enantiomerically enriched cis diol (+)-(1R,2S)-3 and the corresponding 2-acetoxymethyl derivative (+)-(1S,2R)-12 was achieved by lipase PPL-catalyzed transesterification of racemic diol (±)-3.     

Stereochemical aspects of the asymmetric synthesis of chiral α,β-dihydroxy phosphonates. Synthesis of α,β-dihydroxy phosphonic acids

Stereocontrol in the asymmetric phosphonylation of aldehydes via organophosphorous esters has been obtained starting from chiral aldehydes. The nature of the O-protecting group is crucial to obtain, in terms of diastereoselectivity and chemical yields, the best results. An ab initio molecular orbital study on 2-silyloxy propanal and MM2 studies on 2-alkoxy propanal show the existence of stable cyclic and acyclic conformers, which are presumably responsible for the high syn diastereoselectivity observed in the addition of non-metal carrying phosphites.     

Separation and analysis of glycyrrhizin, 18beta-glycyrrhetic acid and 18alpha-glycyrrhetic acid in liquorice roots by means of capillary zone electrophoresis

Glycyrrhizin is the main active compound of Glycyrrhiza glabra root extracts; according to recent studies, glycyrrhizin and its aglycon, glycyrrhetic acid, have interesting therapeutic properties. A new capillary electrophoretic method has been developed for the separation and quantification of glycyrrhizin, beta-glycyrrhetic acid and its isomer a-glycyrrhetic acid. Separation of the analytes was achieved in less than 3 min on a fused silica capillary, by injecting the samples at the short end of the capillary (effective length: 8.5 cm). The background electrolyte was composed of pH 10.0 carbonate buffer, methanol and ethylene glycol (80/10/10) and contained 0.4% beta-cyclodextrin; indomethacin was used as the internal standard. Diode array detection was used, with quantitative assays carried out at 254 nm. Linearity was found over the 5-200 and 2.5-100 microg mL(-1) concentration ranges for glycyrrhizin and glycyrrhetic acid, respectively. This method has been applied to the determination of the analytes in different matrices (liquorice roots and commercial confectionery products), and to the purity control of beta-glycyrrhetic acid obtained from the hydrolysis of glycyrrhizin. When analysing beta-glycyrrhetic acid and its epimer in roots, the samples were purified by means of a suitable solid-phase extraction (SPE) procedure with Oasis HLB cartridges, which granted good selectivity, eliminating matrix interference.     

Metal complexes of C2-symmetric chiral bipyridine ligands. X-ray structure of [bis(nitrato)(4S,5S)-2,2-dimethyl-4,5-bis(2-pyridyl)-1,3-dioxolane cobalt(II)]

Chelating properties of C₂-symmetric chiral bipyridine ligands are discussed. In particular we report the syntheses of the cobalt(II), nickel(II), zinc(II) and copper(II) complexes of (4S,5S)-2,2-dimethyl-4,5-bis(2-pyridyl)-1,3-dioxolane. All compounds have been characterized by IR spectroscopy, and an X-ray diffraction analysis has been carried out on one of them: Co(L)(NO₃)₂. The ligand coordinates the cobalt atom by the two nitrogen donors N(1) and N(2). A seven-membered chelation ring is formed, presenting a remarkable non-crystallographic twofold pseudosymmetry around the axis connecting Co and the midpoint of the C(6)–C(7) bond. The metal also binds two monodentate nitrates, thus completing a distorted coordination tetrahedron.     

Langmuir–Blodgett films of pyridinium-dicyanomethanide dyes mixtures with photobleachable absorption bands

We report on Langmuir-Blodgett (LB) films characterization of 4-[5-dicyanomethanido)thien-2-y1]-N-(n-hexadecyl)pyridinium (C₁₆H₃₃-PDCNT), and 1-(N-(n-hexadecy]-4-pyridinio)-2-[5-(dicyanomethanido)thien-2-yl]ethene (C₁₆H₃₃-PDCNTE); LB films of the pure compounds and of the mixtures of the two compounds were prepared at 291 K: UV-vis investigation revealed the presence of photobleachable absorption bands, the ones at about 530 nm and 640 nm were due to charge transfer transitions of the monomer of C16H33-PDCNT and C₁₆H₃₃-PDCNTE, respectively; the sharp, photobleachable ones shifted to shorter wavelengths were due to H-aggregates of the two compounds. By changing the molar ratios of the two compounds in the mixtures and in other cases by annealing the LB films, the absorption maxima of the sharp, photobleachable bands due to H-aggregates could be tuned in the range 415–467 nm. These LB films are thus very promising in view of optical data storage applications.