Asymmetric alkylation of diarylmethane derivatives. Improved results using methoxyethoxy substituent

Alkylation of 2-methoxyethoxyphenyl phenyl methane using sec-BuLi and (−)-sparteine has been carried out in excellent yields and up to 94% ee. The best results were obtained in allylation reactions but methylation, ethylation, benzylation and trimethylsilylation have all been carried out with acceptable ee.     

Seeding and the Non-Hydrolytic Sol-Gel Synthesis of ZrW2O8 and ZrMo2O8

The unseeded non-hydrolytic sol-gel synthesis of ZrW₂O₈ and ZrMo₂O₈ produces trigonal ZrM₂O₈ (M = W, Mo) at 740 and 300–400°C, respectively. Cubic ZrW₂O₈ can be prepared using non-hydrolytic sol-gel methods by seeding with small amounts of preprepared cubic material, and the formation of the trigonal polymorph can be suppressed completely. Seeds with a small particle size are necessary for the preparation of cubic ZrW₂O₈. In contrast, seeding of ZrMo₂O₈ gels with either cubic ZrMo₂O₈ or cubic ZrW₂O₈ only lowers the temperature at which the trigonal phase crystallizes.     

Diffuse-reflectance laser flash photolysis of 16-(1-pyrene)-hexadecanoic acid adsorbed on silica

The absorption and fluorescence of 16-(1-pyrene)-hexadecanoicacid adsorbed on silica have been investigated. Time-resolved transient diffuse reflectance spectra were recorded following pulsed nanosecond laser excitation at 355 nm of pyrene, 1-methylpyrene and 16-(1-pyrene)-hexadecanoicacid adsorbed on silica. In addition to a rapidly decaying transient, absorbing at 420 nm assigned as the triplet state, and of the radical cation, absorbing at 460 nm, another long living transient species absorbing at 420 nm was observed for 16-(1-pyrene)-hexadecanoic acid. The decay is reversible but complete recovery takes several hours. Although no definitive assignment could be made for this transient several possibilities are discussed. The radical cations of the investigated molecules are formed by a biphotonic process. The non-exponential decay of the radical cations could be analyzed in the framework of a Gaussian distribution of free energy barriers.     

Fermi resonances in the Raman spectra of alkali halide/BH4−

Raman spectra of a series of alkali-halide/BH^?₄ (and BD^?₄ crystals have been obtained. These spectra show some interesting examples of Fermi resonance type interactions between the stretching mode levels and overtone and combination band levels of the bending modes. Two resonances will be considered: (i) that between ν₁ and 2ν₄(A₁), and (ii) that between ν₃, 2ν₄ (F₂) and (ν₂+ν₄) (F₂).The F₂ resonance between ν₃, 2ν₄ and ν₂+ν₄ appears in the infrared spectrum and it has been studied on several occasions. However the equivalent Raman spectrum is of interest because the relative intensities of the bands are significantly different to those shown by the infrared spectrum.In the A₁ (and E) Raman spectrum of the stretching mode region there are two strong bands for each for the ¹⁰B and ¹¹B isotopes. The ν₁ would not be expected to show any ¹⁰B and ¹¹B splitting, but the observed bands are both closely resonating mixtures of ν₁ and 2ν₄(A₁). In fact the analysis shows that the stronger band has the higher proportion of 2ν₄ character, and the larger isotopic shift of the more intense band can then be seen to be reasonable.     

Macrolide antibiotics—VIII The absolute configuration of certain centers in neomethymycin, erythromycin and related antibiotics

Neomethymycin (I) has been transformed into “anhydrocycloneomethynolide” (V) which could be degraded via (−)--methyllevulinic acid to (−)--methylsuccinic acid, thus establishing the absolute configuration of positions 4 and 6 in the lactonic acid (XIII). This acid is a common degradation product of methymycin, neomethymycin, pikromycin and narbomycin and there is thus available a standard of absolute configuration for these macrolide antibiotics. By a different sequence of reactions, erythromycin (XXIII) has been converted into (+)--methyllevulinic acid and (+)--methylsuccinic acid. Coupled with earlier results reported in the literature, it is now possible to assign absolute configurations to positions 10 (R) and 8 (R) of erythromycin and this applies most likely also to positions 4 (R) and 2 (S). Attention is called to the biogenetic significance of these observations.     

The extraordinary ability of guanidinate derivatives to stabilize higher oxidation numbers in dimetal units by modification of redox potentials: structures of Mo(2)(5+) and Mo(2)(6+) compounds

Full characterization of the first homologous series of dimolybdenum paddlewheel compounds having electronic configurations of the types sigma(2)pi(4)delta(x), x = 2, 1, 0, and Mo-Mo bond orders of 4, 3.5, and 3, respectively, has been accomplished with the guanidinate-type ligand hpp (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). Essentially quantitative oxidation of Mo(2)(hpp)(4), 1, by CH(2)Cl(2) gives Mo(2)(hpp)(4)Cl, 2. The halide in 2 can be replaced by reaction with TlBF(4) to produce Mo(2)(hpp)(4)(BF(4)), 3. Further oxidation of 2 by AgBF(4) produces Mo(2)(hpp)(4)ClBF(4), 4. The change from bond order 4 (in 1) to 3.5 in Mo(2)(hpp)(4)Cl is accompanied by an increase in the Mo-Mo bond length of 0.061 to 2.1280(4) A. A further increase of 0.044 A in the Mo-Mo distance to 2.172(1) A is observed as the bond order decreases to 3 in 4. At the same time, the Mo-N distances decrease smoothly as the oxidation state of the Mo atoms increases. Electrochemical studies have shown two chemically reversible processes at very negative potentials, E(1)(1/2)= -0.444 V and E(2)(1/2)= -1.271 V versus Ag/AgCl. These correspond to the processes Mo(2)(6+/5+) and Mo(2)(5+/4+), respectively. The latter potential is displaced by over 1.5 V relative to those of the Mo(2)(formamidinate)(4) compounds and the first one has never been observed in such complexes. Thus, in surprising contrast to previously observed behavior of the dimolybdenum unit, when it is surrounded by the very basic guanidinate ligand hpp, there is an extraordinary stabilization of the higher oxidation numbers of the molybdenum atoms.