From an -Estrane, through a -Androstane, to the Total Synthesis of the Marine-Derived Δ-Pregnene (+)-03219A.

The total synthesis of (+)-03219A, a rare Δ-pregnene isolated from the marine-derived sp. SCSIO 03219, is described that is based on a series of transformations that enable progression from epichlorohydrin to an -estrane, then conversion to a -androstane, and finally establishment of the natural product target. Key to the success of these studies was implementation of two rearrangement processes to formally invert the quaternary center at C13 and establish the C10 quaternary center.

Copper(I) and silver(I) complexes of anthraldehyde thiosemicarbazone: synthesis, structure elucidation, anti-tuberculosis/cytotoxic activity and interactions with DNA/HSA.

A reaction of copper(i) halides (X = I, Br, Cl) and silver(i) halides with 9-anthraldehyde thiosemicarbazone (9-Hanttsc, H1L) and triphenylphosphine produced halogen-bridged dinuclear complexes, [M2(μ2-X)2(η1-S-9-Hanttsc)2(Ph3P)2] (M = Cu, X = Cl, 1; Br, 2; I, 3; M = Ag, X = Cl, 4; Br, 5). A similar reaction of 9-anthraldehyde-N1-methyl thiosemicarbazone (9-Hanttsc-N1-Me, H2L) with Ph3P and silver(i) halides yielded sulfur-bridged dimers, [Ag2X2(μ2-S-9-Hanttsc-N1-Me)2(Ph3P)2] (X = Cl, 9; Br, 10), however with copper(i) halides insoluble compounds were formed, which upon the addition of one extra mole of Ph3P gave mononuclear complexes of the formula [CuX(η1-S-9-Hanttsc-N1-Me)(Ph3P)2] (X = Cl, 6; Br, 7; I, 8). All of the complexes have been characterized by elemental analysis, NMR (1H, 13C) spectroscopy and single crystal X-ray crystallography (2, 5, 6, and 9).

Enhancement in anti-tubercular activity of indole based thiosemicarbazones on complexation with copper(I) and silver(I) halides: Structure elucidation, evaluation and molecular modelling.

A series of monomeric tetrahedral complexes of stoichiometry, [MX(HL)(PhP)] (In case of M = Cu, HL, X = I, 1; Br, 2; Cl, 3; HL, X = I, 4; Br, 5; Cl, 6; HL, X = I, 7; Br, 8; Cl, 9 and in case of M = Ag, HL, X = Cl, 13; Br, 14; HL, X = Cl, 15, Br 16; HL, X = Cl, 17, Br, 18) were synthesized by the reaction of copper (I) or silver (I) halides with indole-3-thiosemicarbazone (HL) or 5-methoxy indole-3-thiosemicarbazone (HL) or 5-methoxy indole-N-methyl-3-thiosemicarbazone (HL), whereas dimers of stoichiometry, [Cu(μ-X)(η-S-HL)(PhP)] (X = I, 10; Br, 11; Cl, 12) were obtained by the reaction of copper (I) halides with indole-N-methyl-3-thiosemicarbazone (HIntsc-N-Me, HL). The synthesized complexes were characterized using NMR (H and C) and single crystal X-ray diffraction (HL, 3, 7, 8, 10, 11 and 13) as well as elemental analysis. Anti- M.

A Highly Chemo-, Regio-, and Stereoselective Metallacycle-Mediated Annulation Between a Conjugated Enyne and an Ene-Diyne.

Alkoxide-directed metal-centered intermolecular [2+2+2] annulation is shown to chemo-, regio-, and stereoselectively engage two polyunsaturated substrate in productive cyclization chemistry. This annulation process is unique in the field, revealing that it is possible to selectively engage three of five π-systems residing in the coupling partners in initial [2+2+2] reaction, and demonstrating that one of the two remaining π-systems (the TMS-alkyne) can ultimately serve to simply generate a new metallacyclopentene of great potential value in additional metallacycle-mediated coupling chemistry.

N-Ethyl-2-[1-(2-hy-droxy-naphthalen-1-yl)ethyl-idene]hydrazinecarbo-thio-amide.

In the title compound, C15H17N3OS, the dihedral angle between the mean planes of the 2-hy-droxy-napthyl ring system and the hydrazinecarbo-thio-amide group is 73.7 (3)°. In the crystal, weak O-H⋯S and C-H⋯O inter-actions and π-π stacking inter-actions involving one of the hy-droxy-napthyl rings with a centroid-centroid distance of 3.