Lanthanum(III) and uranyl(VI) diglycolamide complexes: synthetic precursors and structural studies involving nitrate complexation

The synthesis and structural characterization of lanthanum(III) and uranyl(VI) complexes coordinated by tridentate diglycolamide (DGA) ligands O(CH2C(O)NR2)2[R=i-Pr (L1), i-Bu (L2)] are described. Reaction of L with UO2Cl2(H2O) n forms the uranyl(VI) cis-dichloride adducts UO2Cl2L [L=L1 (1a), L2 (1b)], while reaction of excess L with the corresponding metal nitrate hydrate produces [LaL3][La(NO3)6] [L=L1 (2a), L2 (2b)] for lanthanum and UO2(NO3)2L [L=L1 (3a), L2 (3b)] for uranium. Compounds 2b and 3a have been structurally characterized. The solid-state structure of the cation of 2b shows a triple-stranded helical arrangement of three tridentate DGA ligands with approximate D3 point-group symmetry, while the counteranion consists of six bidentate nitrate ligands coordinated around a second La center. The solid-state structure of 3a shows a tridentate DGA ligand coordinated along the equatorial plane perpendicular to the OUO unit as well as two nitrate ligands, one bidentate and oriented in the equatorial plane and the other monodentate and oriented parallel to the uranyl unit with the oxygen donor atom situated above the mean equatorial plane. Ambient-temperature NMR spectra for 3a and 3b indicated an averaged chemical environment of high symmetry consistent with fluxional nitrate hapticity, while spectroscopic data obtained at -30 degrees C revealed lower symmetry consistent with the slow-exchange limit for this process.     

Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β‐Aminoketone Derivatives

A highly stereoselective route to functionalized pyrrolidines by the metal‐catalyzed diverted N?H insertion of a range of diazocarbonyl compounds with β‐aminoketone derivatives is described. A number of catalysts (rhodium(II) carboxylate dimers, copper(I) triflate, and an iron(III) porphyrin) are shown to promote the process under mild conditions to give a wide range of highly substituted proline derivatives. The reaction starts as a metallocarbene N?H insertion but is diverted by an intermolecular aldol reaction.     

Benzimidazole- and benzothiazole-quinones: excellent substrates for NAD(P)H:quinone oxidoreductase 1

A series of benzimidazole- and benzothiazole-quinones has been synthesized. The ability of these heterocyclic quinones to act as substrates for recombinant human NAD(P)H:quinone oxidoreductase (NQO1), a two-electron reductase upregulated in tumour cells, was determined. Overall, the quinones were excellent substrates for NQO1.     

On the keto-enol tautomerization of malonaldehyde: an effective fragment potential study

Recent studies have mapped the keto-enol tautomerization of malonaldehyde through a general transition structure that leads exclusively to the Z isomer of the enol. However, it will be shown that a competing general transition structure exists that leads to both the E and Z isomers of the enol at the B3LYP/6-31G(d,p) and MP2/6-31G(d,p) levels of theory. Both the RHF- and DFT-based effective fragment potential methods have been used to model solvation effects, and the results are compared with full ab initio calculations. It is found that two bridging water molecules with two discrete DFT-based effective fragment potential solvent waters at the MP2/6-31G(d,p) level of ab initio theory provides the most computationally effective model for solvent effects in this system. It is shown that the relative energies for this QM/MM model differ from the full MP2/6-31G(d,p) energies by an average absolute relative difference of 2.2 kcal mol-1 across the reaction path when the zero-point vibrational energy correction is included.     

The remarkable effect of the 7-substituent in the diastereoselective oxidative rearrangement of indoles: asymmetric synthesis of 3,3-disubstituted oxindoles

The nature of the 7-substituent has a remarkable effect on the diastereoselectivity of the oxidative rearrangement of indole-2-carboxamides derived from (S)-2-methoxymethylpyrrolidine into chiral 3,3-disubstituted oxindoles.     

One-pot synthesis of N-methylindoles from N-methylanilines and of benzofurans from phenols using transition-metal carbene X-H insertion reactions

Transition-metal carbene X-H insertion reactions (X=N or O) have been employed in the simple conversion of anilines and phenols into indoles and benzofurans, respectively. Thus copper(II) catalyzed N-H insertion reactions of α-diazo-β-ketoesters with N-methylanilines followed by treatment with acidic ion-exchange resin gives indoles. In a similar manner, dirhodium(II) catalyzed O-H insertion reactions of α-diazo-β-ketoesters with phenols followed by treatment with PPA gives benzofurans.     

Gamma-rays emitted in the alpha-decay of <Superscript>245</Superscript>Cm

It has been observed that the intensities of the gamma-rays emitted in the alpha-decay of ²⁴⁵Cm reported in the literature result in calculated concentrations that do not agree with those obtained via other methods. In this work, a ²⁴⁵Cm sample was chemically isolated from a sample of ²⁴⁹Cf, and the gamma-ray intensities were measured relative to the alpha-particle emission rate of the resulting source; there is a systematic bias relative to the literature intensities of approximately 8%. In addition, gamma-rays that have never before been observed in the decay of ²⁴⁵Cm are placed in the level scheme of the decay product, ²⁴¹Pu.     

The Diffie–Hellman problem and generalization of Verheul’s theorem

Bilinear pairings on elliptic curves have been of much interest in cryptography recently. Most of the protocols involving pairings rely on the hardness of the bilinear Diffie–Hellman problem. In contrast to the discrete log (or Diffie–Hellman) problem in a finite field, the difficulty of this problem has not yet been much studied. In 2001, Verheul (Advances in Cryptology—EUROCRYPT 2001, LNCS 2045, pp. 195–210, 2001) proved that on a certain class of curves, the discrete log and Diffie–Hellman problems are unlikely to be provably equivalent to the same problems in a corresponding finite field unless both Diffie–Hellman problems are easy. In this paper we generalize Verheul’s theorem and discuss the implications on the security of pairing based systems.