Copper(I) Chloride Mediated Amination of Halobenzenes via Azides: Scope, Mechanistic Aspects, and C-C Cleavage Reactions.

Selective azidation-amination of long-chain alkanoyl halobenzenes with sodium azide, promoted by copper(I) chloride, is reported. The protocol is, apart from CuCl and NaN, additive free and allows the isolation of versatile amine-azides. Alkyl cleavage occurs as a side reaction through an unusual Schmidt-type azide insertion adjacent to the carbonyl group, forming alkyl nitriles possibly via radical pathways.

Bengamides display potent activity against drug-resistant Mycobacterium tuberculosis.

Mycobacterium tuberculosis infects over 10 million people annually and kills more people each year than any other human pathogen. The current tuberculosis (TB) vaccine is only partially effective in preventing infection, while current TB treatment is problematic in terms of length, complexity and patient compliance. There is an urgent need for new drugs to combat the burden of TB disease and the natural environment has re-emerged as a rich source of bioactive molecules for development of lead compounds.

Publisher Correction: A new fundamental type of conformational isomerism.

In the version of this Article originally published, the word 'stereoisomerism' was erroneously included in the label of the upper-right box of Fig. 1. The label within the box has been corrected and it now reads: "Constitutional isomerism (same formula, different connectivity)".

A new fundamental type of conformational isomerism.

Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology.

Synthesis of all-L cyclic tetrapeptides using pseudoprolines as removable turn inducers.

Cyclic tetrapeptides have generated great interest because of their broad-ranging biological properties. In order to synthesize these highly strained 12-membered cyclic compounds, a cyclization strategy using pseudoprolines as removable turn inducers has been developed. The pseudoproline derivatives induce a cisoid amide bond in the linear peptide backbone which facilitates cyclization.

Regioselective reactivity of an asymmetric tetravalent di[dihydroxotin(IV)] bis-porphyrin host driven by hydrogen-bond templation.

Local molecular environment effects on the rates of ligand exchange at an asymmetric di[dihydroxotin(IV)] bis-porphyrin 5 are examined. The host 5 possesses four non-equivalent tin(IV)-ligand binding sites that are distinguished by their position relative to a shallow cavity, by the steric environment at each binding site and by electronic-structure differences between the constituent porphyrin and quinoxalinoporphyrin macrocycles. These design features of the asymmetric host are confirmed by X-ray crystal structure analysis.

Complete 1H and 119Sn NMR spectral assignment for an asymmetric di[dihydroxotin(IV)] bis-porphyrin supramolecular host and its corresponding tetraacetato complex.

The full (1)H and (119)Sn NMR spectral assignments for a di[dihydroxotin(IV)] bis-porphyrin supramolecular host I and for the di[diacetatotin(IV)] complex II are presented. Despite the lack of varied chemical functionality in these molecules, all of their 64 proton environments are non-equivalent. This is due to the asymmetry afforded by the Tröger's base (methanodiazocine) bridge between the porphyrin and quinoxalinoporphyrin macrocycles.

Ruthenium complexes of analogues of the antitumor antibiotic streptonigrin.

The complexes Ru(L1-CH3)(CO)3Cl, RuL2(CO)2Cl2, and RuL3(CO)2Cl2 (L1= 6-methoxy-5,8-quinolinedione, L2 = 7-amino-6-methoxy-5,8-quinolinedione, L3 = 6,6'-dimethoxycarbonyl-2,2'-bipyridine) were prepared by reaction of L1-L3 with the tricarbonyldichlororuthenium(II) dimer. L1-L3 act as bidentates through the ortho oxygen atoms, the pyridyl nitrogen and the adjacent quinone oxygen, and the bipyridyl nitrogens, respectively. RuL3(CO)2Cl2 is characterized by X-ray crystallography.