Studies into the Diels-Alder reactions of 5-trimethylsilylthebaine

The introduction of a 5-trimethylsilyl group on the least hindered face of the diene thebaine was anticipated to favor attack by dienophiles from the alternate face, but only gave rise to a rearrangement product when treated with 3-butene-2-one at 110 °C. Reaction with the more reactive benzoquinone at lower temperature gave rise to a very slow reaction from the same face as the silyl group, indicating that a trimethylsilyl group does not sufficiently hinder this face to achieve reaction at the other face.     

In situ electrochemical ESR and voltammetric studies on the anodic oxidation of para-haloanilines in acetonitrile

An in situ electrochemical electron spin resonance (ESR) study on the electro-oxidation of para-chloroaniline, para-bromoaniline, and para-iodoaniline dissolved in acetonitrile at gold electrodes is reported. ESR spectra obtained using a tubular flow cell reveal the presence of a paramagnetic dimer product derived from para-aminodiphenylamine, during oxidative electrolysis, suggesting the coupling of reactive electrogenerated radical cations with neutral parent haloaniline molecules. The ESR signal intensity behaves in a manner expected for a radical species reacting with second-order kinetics, suggesting the paramagnetic dimer is, itself, unstable. The theory describing the ESR signal intensity flow rate behavior for this reaction mechanism is developed for the tubular arrangement and used to extract mechanistic and kinetic data from the experimental results for the cases of para-chloroaniline and para-bromoaniline. Further mechanistic aspects, including proton and halide ion expulsion during dimerization, are explored voltammetrically and with the aid of digital simulations using Digisim. Comparison of the ESR signal and voltammetric measurements suggests that an additional mechanism operates which does not lead to paramagnetic products. Additionally, the in situ electrolysis of N,N-dimethyl-para-bromoaniline is reported to generate the stable radical cation of N,N,N',N'-tetramethylbenzidine, and a mechanism of electro-oxidation is, thus, proposed.     

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO (peroxynitrous acid). The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple zeta basis set, at the structure optimized using the triple zeta basis set (CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ). The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD(T)/cc-pVTZ and QCISD/AUG-cc-pVTZ (QCISD-quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions) level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at approximately 90 degrees , the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2nu(OH) region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+NO(2) and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D(0)=82.0 kJ/mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to Deltan=0 transitions (where n is the HOON torsion quantum number) that are blue shifted relative to the origin band, while the large peak near 7000 cm(-1) is assigned to a series of Deltan=+1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO (6300-6850 cm(-1)) is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm(-1) and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations.     

Synthesis of a deca-lithium cage containing an [(RN)2As(mu-NR)As(NR)2]4- tetraanion; a homologue of group 15 trianions of the type [E(NR)3]3-

The novel, deca-lithium cage [(mtaNHLi)(As2(Nmta)5)-Li(4).2thf]2 (1) (mtaN = 5-methylthiazolyl, C4H4N2S) contains an imido-bridged tetraanion [(mtaN)2As(mu-Nmta)-As(Nmta)2]4-, which represents a new type of multi-functional imido group 15 ligand framework (homologous with group 15 anions of the type [As(NR)3]3-).     

The ene reactions of nitroso compounds involve polarized diradical intermediates

The ene reactions of nitroso compounds were studied with B3LYP/6-31G* geometry optimizations and energy calculations, along with single point energy evaluations using CASPT2/6-31G** and UCCSD(T)/6-311+G* methods. Reactions of HNO with propene and of MeNO and p-NO2C6H4NO with propene or substituted alkenes were also studied. The reaction mechanism is stepwise and involves a polarized diradical intermediate. The electronic structure of this intermediate is between that of a closed shell polar species and that of a pure diradical, and it is stabilized by polar solvents. A weak C-N bonding interaction combined with a CH-O hydrogen bond leads to heightened barriers to rotation about formally single bonds compared to conventional diradicals. Consequently, rotation is slower than hydrogen abstraction and cyclization to form an aziridine N-oxide. This aziridine N-oxide does not lead to ene products without subsequent ring opening but provides a mechanism for the RNO moiety to translate from one end of the alkene to the other. B3LYP calculations are also able to reproduce kinetic isotope effects and regioselectivity.     

Synthesis and reactivity of dimeric Ar'TlTlAr' and trimeric (Ar"T1)3 (Ar', Ar" = bulky terphenyl group) thallium(I) derivatives: Tl(I)-Tl(I) bonding in species ligated by monodentate ligands

The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons.     

Fast atom bombardment mass spectra of involatile monophosphonated and mixed sulphonated/monophosphonated azo dyestuffs

Fast atom bombardment mass spectra of a range of involatile monophosphonated and mixed sulphonated/monophosphonated azo dyestuffs are presented. Good spectra are obtained and the fragmentations are discussed with special reference to the ions formed by cleavage of the azo linkage. The negative ion spectra are shown to be superior in terms of signal to background and structural information to those obtained in the positive ion mode. The results are compared with those obtained from sulphonated azo dyestuffs.     

Assessing the efficiency of free energy calculation methods

The efficiencies of two recently developed methods for calculating free energy changes along a generalized coordinate in a system are discussed in the context of other, related approaches. One method is based on Jarzynski's identity [Phys. Rev. Lett. 78, 2690 (1997)]. The second method relies on thermodynamic integration of the average force and is called the adaptive biasing force method [Darve and Pohorille, J. Chem. Phys. 115, 9169 (2001)]. Both methods are designed such that the system evolves along the chosen coordinate(s) without experiencing free energy barriers and they require calculating the instantaneous, unconstrained force acting on this coordinate using the formula derived by Darve and Pohorille. Efficiencies are analyzed by comparing analytical estimates of statistical errors and by considering two numerical examples-internal rotation of hydrated 1,2-dichloroethane and transfer of fluoromethane across a water-hexane interface. The efficiencies of both methods are approximately equal in the first but not in the second case. During transfer of fluoromethane the system is easily driven away from equilibrium and, therefore, the performance of the method based on Jarzynski's identity is poor.     

Stereoselective synthesis of the cyclic ether core of (+)-laurenyne

A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction.     

A convenient synthesis of cis and trans 4-tert-butoxycarbonyl-substituted cyclohexylglycine

A novel synthesis of cis and trans substituted 4-tert-butoxycarbonyl cyclohexylglycines via asymmetric aminohydroxylation of vinyl styrene followed by reduction of the aromatic ring and subsequent oxidation is reported.