Catalytic enantioselective synthesis of vicinal dialkyl arrays

With a consecutive "asymmetric allylic alkylation (AAA)/cross-metathesis (CM)/conjugate addition (CA)" protocol it is possible to synthesize either stereoisomer of compounds containing a vicinal dialkyl array with excellent stereoselectivity. The versatility of this protocol in natural product synthesis is demonstrated in the preparation of the ant pheromones faranal and lasiol.     

1,3-Diol synthesis via controlled, radical-mediated C-H functionalization

The invention of a method for the synthesis of 1,3-diols from the corresponding alcohols is described, via controlled, radical-mediated C-H functionalization. The sequence described herein entails near quantitative conversion to the corresponding trifluoroethyl carbamate, followed by a variant of the Hofmann-L?ffler-Freytag reaction, cyclization, and hydrolysis to provide the 1,3-diols. In addition to the 10 examples presented herein, the syntheses of four natural products are facilitated by this directed oxyfunctionalization. This methodology is demonstrated to be orthogonal to other known C-H oxidations. Finally, this sequence is efficient, practical, inexpensive, and scalable.     

Coordination asymmetry in divanadium(V) compounds containing a V2O3 core: synthesis, characterization, and redox properties

A general protocol for the synthesis of micro-oxo divanadium(V) compounds [LOV(micro-O)VO(Salen)] (1-5) incorporating coordination asymmetry has been developed for the first time. One of the vanadium centers in these compounds has an octahedral environment, completed by tetradentate Salen ligand, while the remaining center has square pyramidal geometry, made up of tridentate biprotic Schiff-base ligands (L2-) with ONO (1-3) and ONS (4, 5) type donor combinations. Single crystal X-ray diffraction analysis, ESI-MS, and NMR (both 1H and 51V) spectroscopy have been used extensively to establish their identities. The V(1)-O(6)-V(2) bridge angle in these compounds, save 3, lie in a narrow range (166.20(9)-157.79(16) degrees) with the V2O3 core having a rare type of twist-angular structure, somewhat intermediate between the regular anti-linear and the syn-angular modes. For 3, however, the bridge angle is sufficiently smaller 117.92(8) degrees that it forces the V2O3 core to adopt an anti-angular geometry. The V(1)...V(2) separations in these molecules (3.7921(7)-3.3084(6) A) are by far the largest compared to their peers containing a V2O3 core. The molecules retain the binuclear structures also in solution as confirmed by NMR spectroscopy. Their redox behaviors appear quite interesting, each undergoing a one-electron reduction in the positive potential range (E1/2, 0.42-0.45 V vs Ag/AgCl) to generate a trapped-valence mixed-oxidation products [LVVO-(micro-O)-OVIV(salen)]1-, confirmed by combined coulometry-EPR experiments. The bent V-O-V bridge in these molecules probably prevents the symmetry-constrained vanadium d xy orbitals, containing the unpaired electron, to overlap effectively via the ppi orbitals of the bridging oxygen atom, thus accounting for the trapped-valence situation in this case.     

The Self-Association and Mixed Micellization of an Anionic Surfactant,Sodium Dodecyl Sulfate,and a Cationic Surfactant,Cetyltrimethylammonium Bromide: Conductometric,Dye Solubilization,and Surface Tension Studies

In the present study, we investigate the self-association and mixed micellization of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of SDS, CTAB, and mixed (SDS + CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C₂₀ (the surfactant concentration required to reduce the surface tension by 20 mN/m), Π_CMC (the surface pressure at the CMC), Γ_max (maximum surface excess concentration at the air/water interface), and A_min (the minimum area per surfactant molecule at the air/water interface)) of SDS, CTAB, and (SDS + CTAB) micellar/mixed micellar systems were evaluated. The thermodynamic parameters of the micellar (SDS and CTAB), and mixed micellar (SDS + CTAB) systems were evaluated.

A schematic representation of micelles and mixed micelles.     

A pyrazolate-supported Fe(3)(mu(3)-O) core: structural, spectroscopic, electrochemical, and magnetic study

A comparison is made between the structural, spectroscopic, electrochemical, and magnetic properties of pyrazolate versus carboxylate complexes [Fe3(mu3(mu3O)(mu-LL)6Cl3]2- containing the Fe3(mu3-O)-motif. While the Fe3(mu3-O)-cores are structurally indistinguishable in the two types of complexes, their magnetic properties deviate from the expected values as a result of a through-pyrazole contribution to the overall antiferromagnetic exchange with J1/hc = -80.1 cm(-1) and J2/hc = -72.4 cm(-1), or J1/hc = 70.6 cm(-1) and J2/hc = -80.8 cm(-1), (Hex = -J1(S1S2 + S2S3) - J2S1S3). The magnetic properties of the pyrazolate complexes are further tuned by an antisymmetric exchange interaction term.     

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH₃, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH₃ so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.     

Characterization of Two New Copper(II) Complexes with Saccharinate and Benzimidazole as Ligands

The crystal structure of the complexes [Cu(sac)₂(bzim)₂(H₂O)] ( 1 ) and [Cu(sac)₂(bzim)(H₂O)(EtOH)] · 2 EtOH ( 2 ) (sac = saccharinate anion; bzim = benzimidazole; EtOH = ethanol) was determined by single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic C2/c space group with Z = 8 whereas complex 2 belongs to the triclinic P1 space group with Z = 2. Room temperature magnetic susceptibilities as well as electronic and IR spectra of both complexes were discussed. Their thermal behaviour was investigated by means of TG and DTA methods.     

The solvent effects in the reactions of carboxylic acids with oxiranes. 1. Kinetics of the reaction of acetic acid with epichlorohydrin in butan‐1‐ol

Kinetics of the reaction of acetic acid with epichlorohydrin in the presence of chromium(III) acetate in butan‐1‐ol solution have been studied. The partial reaction orders with respect to reagents were found. The reactions were of first‐order with respect to both epichlorohydrin and catalyst and zeroth order with respect to acetic acid. A kinetic model for the overall process has been proposed. The reaction constants have been calculated along with the activation parameters. The effect of dilution on the rate of addition is discussed. In the equimolar mixture of acetic acid and epichlorohydrin the apparent rate constant of the addition k₁ initially decreases to increase again at the concentration of butan‐1‐ol exceeding 3 M. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 378–387, 2000