Ozonolysis of tetramethylethylene: characterization of cyclic and open-chain oligoperoxidic products

The ozonolysis of tetramethylethylene (TME) in solution to high conversion in nonparticipating solvents at -60 degrees C yields predominantly oligoperoxides. For the first time, these products have been characterized using electrospray ionization mass spectrometry (ESI-MS) under soft ionization conditions. The predominant structure formed in reactions carried out in pentane (up to 2.0 M TME) is shown to be the cyclic hexamer of acetone carbonyl oxide (oligocarbonyl oxide with degree of polymerization, n = 6), but cyclic structures with n up to 19 are observed. A small proportion of the oligoperoxides formed are open-chain compounds with end groups that suggest that chain termination of oligocarbonyl oxides can occur through reaction with either water or hydrogen peroxide. Ozonolysis in dried butyl acetate similarly produces mainly cyclic oligoperoxides. However, ozonolyses carried out in undried butyl acetate yield mainly open-chain oligoperoxides, confirming that propagating carbonyl oxide chains are readily terminated by water. Relative amounts of the open-chain oligomers so-formed suggest that undried butyl acetate contains ca. 0.1% w/w water. The ozonolysis of TME in the participating solvent, methanol, at -60 degrees C yields 2-methoxyprop-2-yl hydroperoxide via reaction of acetone carbonyl oxide with methanol; no oligoperoxidic products are formed in this case.     

A re‐examination of supra­molecular aggregation in two polymorphs of acetone 2,4‐dinitro­phenyl­hydrazone

The structure of the triclinic polymorph of acetone 2,4‐dinitrophenylhydrazone, C₉H₁₀N₄O₄, has been redetermined from diffraction data collected at 120 (2) K; the mol­ecules are linked by C—H⋯O hydrogen bonds into centrosymmetric R₂²(10) dimers which are themselves linked into a chain by an aromatic π–π stacking inter­action. In the monoclinic polymorph, which crystallizes with Z′ = 2 in the space group P2₁/n, one type of mol­ecule forms dimers exactly as in the triclinic polymorph, while the other forms C(6) chains.     

Heterometallic Ln/Hg compounds with fluorinated thiolate ligands

The early lanthanide benzenefluorothiolates (Ln(SC(6)F(5))(3); Ln = La, Ce, Pr, Nd, Sm, Gd) react with Hg(SC(6)F(5))(2) in DME to form ionic heterometallic compounds with Ln cations and Hg anions. X-ray diffraction analyses of all compounds reveal an isostructural series with the general formula [(DME)(3)Ln(SC(6)F(5))(2)](2)[Hg(2)(SC(6)F(5))(6)]. In the structures, a fluorothiolate ligand has been extracted from the Ln coordination sphere that is saturated with three neutral DME donor ligands and a dative interaction between one ortho fluorine and the Ln. Distances between Ln and F do not vary simply with Ln ionic radius. There are two Ln cations with charge balanced by a Hg(2)(SC(6)F(5))(6) dianion composed of two distinctly nonideal Hg(II) tetrahedra, all connected through a series of pi-pi interactions that link cations with anions in a one-dimensional array and anions to anions in a more complex 2D network.     

Spontaneously formed unilamellar vesicles with path-dependent size distribution

We observe the spontaneous formation of path-dependent monodisperse and polydisperse phospholipid unilamellar vesicles (ULV) from two different equilibrium morphologies specifically, disklike micelles and extended lamellae, respectively. On heating beyond a temperature Tc, low temperature disklike micelles, or so-called bicelles, transform into lamellae. Dilution of the lamellar phase, at a fixed temperature, results in a complete unbinding transition and the formation of polydisperse ULV, demonstrating the instability of the lamellar phase. On the other hand, heating of a dilute bicellar phase above Tc results in monodisperse ULV, which on cooling revert back to bicelles for lipid concentrations phi > or = 0.5 wt % and transform into oblate ellipsoids for phi = 0.1 wt %, a morphology not previously seen in "bicellar" lipid mixtures. Monodisperse ULV reform on heating of the oblate ellipsoids.     

P(i-BuNCH2CH2)3N: an efficient promoter for the nucleophilic aromatic substitution reaction of aryl fluorides with aryl TBDMS (or TMS) ethers

[reaction: see text]. The nucleophilic aromatic substitution reaction between electron-deficient aryl fluorides and aryl TBDMS (or TMS) ethers has been shown to be efficiently promoted by proazaphosphatranes such as P(i-BuNCH(2)CH(2))(3)N (3). Excellent yields of diaryl ether products were obtained under unusually mild conditions.     

Identification of an activated catalyst in the iridium-catalyzed allylic amination and etherification. Increased rates, scope, and selectivity

Studies were conducted to determine possible intermediates in the highly enantioselective, iridium-catalyzed amination and etherification of allylic carbonates, and these studies revealed that cyclometalation of the phosphoramidite ligand is likely to generate the active catalyst. The square-planar [Ir(COD)(L1)Cl] (L1 = P(BINOL)(bisphenethylamine)) did not react with cinnamyl carbonate, but did react with amine to generate an Ir(I) trigonal bipyramidal complex coordinated by COD, a cyclometalated kappa2-phosphoramidite, and a kappa1-phosphoramidite. This complex reacted with phosphines to generate products from replacement of the kappa1-phosphoramidite. These cyclometalated complexes were highly active catalysts for allylic amination and etherification and retained the high selectivity of the original catalyst system. In addition, these complexes combined with [Ir(cod)Cl]2 catalyzed reactions of amines with lower loadings, catalyzed reactions of alkylamines and aromatic amines that did not react with the original catalyst system, and catalyzed reactions of phenoxides under milder conditions.     

Synthesis of variolin B

The total synthesis of variolin B from 4-methoxy-7-azaindole is described. The preparation of the protected amino derivative 10 and a coupling reaction of the iodo derivative 12 with 2-acetylamino-4-trimethylstannylpyrimidine are the key steps of the sequence. The use of N-tosyldichloromethanimine for the cyclisation step afforded a good entry to the 9-aminopyrido[3′,2′:4,5]pyrrolo[1,2-c]pyrimidine system. Variolin B was obtained from the triply protected tetracyclic compound 13 in two steps.     

Activation volume measurement for C[bond]H activation. Evidence for associative benzene substitution at a platinum(II) center

The reaction of the platinum(II) methyl cation [(N-N)Pt(CH(3))(solv)](+) (N-N = ArN[double bond]C(Me)C(Me)[double bond]NAr, Ar = 2,6-(CH(3))(2)C(6)H(3), solv = H(2)O (1a) or TFE = CF(3)CH(2)OH (1b)) with benzene in TFE/H(2)O solutions cleanly affords the platinum(II) phenyl cation [(N-N)Pt(C(6)H(5))(solv)](+) (2). High-pressure kinetic studies were performed to resolve the mechanism for the entrance of benzene into the coordination sphere. The pressure dependence of the overall second-order rate constant for the reaction resulted in Delta V(++) = -(14.3 +/- 0.6) cm(3) mol(-1). Since the overall second order rate constant k = K(eq)k(2), Delta V(++) = Delta V degrees (K(eq)) + Delta V(++)(k(2)). The thermodynamic parameters for the equilibrium constant between 1a and 1b, K(eq) = [1b][H(2)O]/[1a][TFE] = 8.4 x 10(-4) at 25 degrees C, were found to be Delta H degrees = 13.6 +/- 0.5 kJ mol(-1), Delta S degrees = -10.4 +/- 1.4 J K(-1) mol(-1), and Delta V degrees = -4.8 +/- 0.7 cm(3) mol(-1). Thus DeltaV(++)(k(2)) for the activation of benzene by the TFE solvento complex equals -9.5 +/- 1.3 cm(3) mol(-1). This significantly negative activation volume, along with the negative activation entropy for the coordination of benzene, clearly supports the operation of an associative mechanism.     

AQUEOUS AGGREGATES OF BACTERIOCHLOROPHYLL c AS A MODEL FOR PIGMENT ORGANIZATION IN CHLOROSOMES

Chlorosomes isolated from Chloroflexus aurantiacus were extracted with chloroform/methanol. The extract contained bacteriochlorophylls c and a and lipids, but was devoid of proteins. This crude extract spontaneously formed aggregates when a methanol solution was dispersed in aqueous buffer. The aggregates could be sedimented by ultracentrifugation and appeared in electron micrographs as stain-excluding bodies with diameters between 70 and 170 nm. The absorption spectrum is remarkably similar to that of intact chlorosomes with an absorption maximum of bacteriochlorophyll c at around 740 nm. The circular dichroism spectrum of the aggregate is also very similar to that of intact chlorosomes. A conservative (±) band centered at 740 nm confirms the highly aggregated state of bacteriochlorophyll c in both systems. Steady-state fluorescence studies showed that in the aggregate energy-transfer from bacteriochlorophyll c to a component emitting at 830 nm took place. When the aggregate was suspended in buffer saturated with 1-hexanol the 740 nm form of bacteriochlorophyll c was reversibly converted to a form with spectral properties resembling the monomer absorbing at 670 nm but still in an aggregated state. This form of bacteriochlorophyll c showed no circular dichroism signal.     

Conformational analysis of 1,1,2,2-tetraaryl-disilanes

A study of the static stereochemistry of 1,1,2,2-tetraphenyldisilane (1) and 1,1,2,2-tetramesityldisilane (2) by empirical force field calculations, X-ray diffraction, and ¹H NMR reveals that the preference for the anti conformation, exhibited by the unclamped 1,1,2,2-tetraarylethanes, is sustained in the analogous disilanes, although in somewhat attenuated form. This anti preference stands in contrast to the gauche preference of 1,1,2,2-tetraalkyldisilanes. Examination of ³J_HH coupling constants for R₂HSiSiHR₂; (R = phenyl, mesityl, 2,6-dimethyl-phenyl, t-butyl, cyclohexyl) suggests the existence of a Karplus relation for H-Si-Si-H systems.