Studies on chromium(III) complexes of some new dithiocarbamato ligands

Summary Tris-chelates of chromium(III) have been synthesised with five new dithiocarbamates, [RR'NCS₂]^–, where R=PhCH₂ and R/t'=H, PhCH₂, Me, Et and i-Pr. Magnetic moments together with electronic, i.r. and e.s.r spectra of the complexes have been described. Various ligand-field parameters have been evaluated and discussed.     

Variable electronegativity SCF-MO calculations on the electronic structure and spectra of some substituted benzenes I. Monosubstitutions

π-electron SCF-MO theory in its variable electronegativity formalism has been applied to some monosubstituted benzenes. Calculated charge densities and bond orders for the ground and the first excited electronic states are correlated with chemical reactivity and the changes in molecular geometry on electronic excitation. The calculated results for spectra are compared with those obtained using the PPP method and also with the available experimental data.     

Differentiation of Boc- alpha,beta- and beta,alpha-peptides and a pair of diastereomeric beta,alpha-dipeptides by positive and negative ion electrospray tandem mass spectrometry (ESI-MS/MS)

Positive and negative ion electrospray ionization (ESI) tandem mass spectral study of a new series of hybrid peptides, viz, BocN-alpha,beta-peptides and BocN-beta,alpha-peptides, synthesized from C-linked carbo-beta3-amino acids [Caa (S)] and L-Ala has been carried out. The alpha,beta-peptides have been differentiated from beta,alpha-peptides by the collision-induced dissociation (CID) of [M + H]+ and [M - H]- ions in positive and negative ion ESI-MS respectively. The fragment ion [M + H - C(CH3)3 + H]+ formed from [M + H]+ ions by the loss of 2-methyl-prop-2-ene in alpha,beta-peptides with L-Ala at the N-terminus is insignificant or totally absent for beta,alpha-peptides which have the Caa (S) at N-terminus. The fragment ion [M - H-C(CH3)3OH - HNCO]- formed from [M - H]- of beta,alpha-peptide acids is totally absent for alpha,beta-peptide acids. This has been attributed to the absence of the beta-methylene group in alpha,beta-peptides, and the participation of the beta-methylene group in the loss of HNCO in beta,alpha-peptide acids is confirmed by the deuteration experiments. The CID of [M + H-Boc + H]+ ions of these peptides also produce characteristic fragmentation. In the CID spectra of alpha,beta-peptides, the b(n)+ ions and the resulting y(n)+ ions occur at a mass difference of 243 and 71 Da corresponding to the successive losses of Caa and L-Ala, whereas a mass difference of 71 and 243 Da is observed for beta,alpha-peptides. In contrast to the CID of protonated peptides, the CID of [M - H]- ions of the alpha,beta- and beta,alpha-peptide acids do not give b(n)- ions and show abundant z(n) (-) ions. Further, a pair of diastereomeric dipeptide esters and acids have been distinguished by the CID of [M + H]+ ions. The loss of 2-methyl-prop-2-ene is more pronounced for Boc-NH-Caa(R)-D-Ala-OCH3 (21) and Boc-NH-Caa(R)-D-Ala-OH (23) with Caa (R) at the N-terminus, whereas it is totally absent for Boc-NH-Caa (S)-D-Ala-OCH3 (22) and Boc-NH-Caa(S)-D-Ala-OH (24) peptides, which have Caa (S) at the N-terminus. Thus, on the basis of our previous and present studies, we propose that the CID of [M + H]+ ions provides a simple and useful method for distinguishing the configuration of Caa (S or R) at the N-terminus of BocN-carbo beta,alpha- and beta,beta-dipeptides.     

Rh(i)-catalyzed stereoselective desymmetrization of prochiral cyclohexadienones via highly exo-selective Huisgen-type [3 + 2] cycloaddition

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed. This method enables convergent construction of complex epoxy-bridged polycyclic ring systems with five contiguous stereocenters with excellent exo-selectivity and broad substrate scope. The highly atom-economical process involves 6-endo-dig cyclization of carbonyl oxygen onto an activated alkyne resulting in a highly reactive metal–benzopyrylium intermediate, which readily undergoes intramolecular [3 + 2] annulation/hydration. Asymmetric induction is also achieved for the first time in Rh(i)-catalyzed 1,3-dipolar cycloaddition using an easily accessible chiral diene as the ligand.

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed.     

Studies towards the total synthesis of (−)-borrelidin: a strategy for the construction of the C11-C15 cyanodiene fragment and the utility of RCM for macrocyclization using model systems

We report here a methodology for the construction of a conjugated cyanodiene synthon and the propensity of such synthons to participate in the olefin metathesis reaction. To this end, we have developed a strategy for the construction of the C11-C15 fragment of borrelidin and demonstrated the utility of the RCM reaction in the preparation of the final macrolide. To our knowledge, this is the first example of a RCM with a nitrile functionality on a diene.     

A versatile and practical synthesis of bis(indolyl)methanes/bis(indolyl)glycoconjugates catalyzed by trichloro-1,3,5-triazine

A practical and efficient electrophilic substitution reaction of indoles with a variety of aldehydes was carried out using catalytic trichloro-1,3,5-triazine (10 mol %) in acetonitrile to furnish the corresponding bis(indolyl)methanes in excellent yields. Similarly, sugar derived aldehydes gave hitherto unknown bis(indolyl)glycoconjugates in very good yields.     

Binding energy of lithium halide molecules

A semi-empirical open shell model of sigma bonded systems has been employed to calculate the binding energies for diatomic lithium halides. The repulsion between the atomic cores is taken as the Coulomb repulsion term $\text{1}\text{R}{}_{12}$ modified by the presence of electronic cores. This modification has been estimated from the repulsion term in the Rittner potential function. The agreement with the experimental values is quite satisfactory but the extension of the same method to alkali hydrides results in gross discrepancies. The results are discussed in the light of other results.     

Thin-layer chromatography of hydroxyanthraquinones in plant extracts

Summary Existing thin-layer chromatographic (TLC) methods for the separation of hydroxyanthraquinones in plant materials were found to have limited applications. This initiated the development of some new TLC systems to separate the five principal hydroxyanthraquinones: chrysophanol, physcion, emodin, rhein and aloe emodin normally present together in plant materials, on a single chromatogram and usually with a single solvent system.     

π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

Studies on polymerization of vinyl acetate using ylide as an initiator and degradative transfer agent

Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol^?1. An average value of k/k_t for the present system was found to be 0.37 × 10^?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular.