New Protocol for the Synthesis of S-Thioesters from Benzylic, Allylic and Tertiary Alcohols with Thioacetic Acid.

A new one-pot solvent-less reaction to convert benzylic, allylic, ferrocenyl or tertiary alcohols into S-thioesters, bench-stable and less odorous precursors of the corresponding thiols, which is based on reactions in neat thioacetic acid in the presence of tetrafluoroboric acid, is presented. Reaction monitoring by NMR and GC of the benzyl alcohol conversion indicated the intermediate formation of benzyl acetate and benzyl thionoacetate (PhCH OC(S)CH ) prior to the slower conversion to the final S-benzyl thioacetate product. Increasing the HBF concentration enhanced the reaction rate, giving good to excellent yield (up to 99 %) for a large scope of alcohols.

Acetate exchange mechanism on a Zr oxo hydroxo cluster: relevance for reshaping Zr-carboxylate coordination adaptable networks.

The kinetics and mechanism of the acetate ligand exchange with free acetic acid in [ZrO(OH)(OCCH)], used as a molecular model of crosslink migration in [ZrO(OH)(carboxylate)(OH)]-based coordination adaptable networks with vitrimer-like properties, has been thoroughly investigated by dynamic H NMR and DFT calculations. The compound maintains its -symmetric Zr structure in CDCl and CD, while it splits into its Zr subunits in CDOD and DO. In the Zr structure, the topologically different acetates (3 chelating, 6 belt-bridging, 2 intercluster-bridging and 1 inner-face-bridging) of the Zr subunits behave differently in the presence of free CHCOOH: very fast exchange for the chelating (coalesced resonance at room temperature), slower exchange for the belt-bridging (line broadening upon warming), no observable exchange up to 65 °C (by EXSY NMR) for the intercluster- and inner-face-bridging.

Synthesis and crystal structure of [( )-(2-phenyl-ferrocen-yl)meth-yl]tri-methyl-ammonium iodide di-chloro-methane monosolvate.

As a follow-up to our research on the chemistry of disubstituted ferrocene derivatives, the synthesis and the structure of the title compound, [Fe(CH)(CHN)]I·CHCl, is described. The cation mol-ecule is built up from a ferrocene disubstituted by a tri-methyl-ammonium methyl group and a phenyl ring. The asymmetric unit contains the iodide to equilibrate the charge and a disordered di-chloro-methane solvate.

Iodine-promoted insertion of the oxygen atom from water in η-vinylketene[Fe(CO)] complexes.

Iodine promotes the formation of iron(II) species from η-vinylketene[Fe(CO)] (3a-h) as a key intermediate for the synthesis of 2(5)-furanones (4a-h) by a sequential water-insertion/carbon-oxygen coupling under mild reaction conditions. Compounds 4a-h were obtained in good to excellent yields. A possible reaction pathway was also proposed by DFT calculations.

Interrupted Intramolecular Hydroaminomethylation of -Protected-2-vinyl Anilines: Novel Access to 3-Substitued Indoles or Indoline-2-ols.

A new synthetic alternative to the synthesis of 3-methyl indoles and 3-methyl indoline-2-ols with an excellent atomic economy is presented in this study. It is demonstrated that the intramolecular interrupted hydroaminomethylation (HAM) reaction is a powerful tool for the formation of these compounds, which exhibit wide-ranging biological activity. Several -Protected-2-vinyl anilines were synthesized and involved in the reaction producing the corresponding 3-methylindole or 3-methyl indoline-2-ol depending on the nature of the -protecting groups.

Replacement of Volatile Acetic Acid by Solid SiO@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand.

Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CHCOOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by (nano)particles with two different sizes to which pending carboxylic functions were added (). The beads were obtained by the functionalization of SiO with pending nitrile functions () followed by CN hydrolysis.

Synthesis and crystallographic studies of 2-(di-phenyl-phosphino-thio-yl)-2-(3-oxobut-1-en-yl)ferrocene.

As a follow-up to our research on the chemistry of disubstituted ferrocene derivatives, the synthesis and the structure of the title compound, 2-(di-phenyl-phosphino-thio-yl)-2-(3-oxobut-1-en-yl)ferrocene, [Fe(CH)(CHOPS)], are described. The mol-ecule is built up from a ferrocene unit disubstituted by an S-protected di-phenyl-phosphine group and by a methyl-vinyl-ketone chain. The crystal structure features weak C-H⋯O and C-H⋯S inter-actions, which build a two-dimensional network.

Erratum: -{[2-(Diphenyl-thio-phosphor-yl)ferrocen-yl]meth-yl}dimethyl-ammonium diphenyl-dithio-phosphinate. Corrigendum.

[This corrects the article DOI: 10.1107/S1600536812009129.].

A new P,S-coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with Pd and Pt. Corrigendum.

In the paper by Mouas Toma et al. [Acta Cryst. (2014), C70, 460-464], there was an error in the name of the first author.

Crystal structure of ()-5-[()-3-(4-chloro-phen-yl)-5-methyl-4,5-di-hydro-isoxazol-5-yl]-2-methyl-cyclo-hex-2-enone.

The title compound, CHClNO, was prepared and isolated as a pure diastereoisomer, using column chromatography followed by a succession of fractional crystallizations. Its exact structure was fully identified H NMR and confirmed by X-ray diffraction. It is built up from a central five-membered di-hydro-isoxazole ring to which a -chloro-phenyl group and a cyclo-hex-2-enone ring are attached in the 3 and 5 positions.

Synthesis of -Alkyl Phosphinocarbodithioates with Switch between P(III) and P(V) Derivatives.

Simple and effective synthetic pathways are described to prepare compounds RP(X)C(S)SCH(Me)Ph with the P atom either in the oxidation state V [R/X = Bu/O (), Ph/S, (), Bu/S (), Bu/Se ()] or III [R/X = Ph/BH (), Bu/BH (), Bu/lone pair ()]. Compound is the first example of carbodithioate ester with a P = Se group, and for the first time, a phosphinocarboditioate with a free phosphine function (compound ) is described. Stabilization of the latter crucially depends on the steric protection by the Bu groups since an analogous derivative with R = Ph is observable but too unstable for isolation.

Crystal structure of penta-carbon-yl(2,2-di-fluoro-propane-thio-ato-κ)manganese(I).

The title compound, [Mn{SC(O)CFCH}(CO)], has been isolated as a by-product during the reaction of K[Mn(CO)] with CHCFCOCl. It is built up from a di-fluoro-methyl-propane-thio-ate bonded to an Mn(CO) moiety through the S atom. The Mn atom has an almost perfect octa-hedral coordination sphere.

A triangular palladium(II) supramolecular coordination complex based on 1,4-bis(1H-imidazol-1-yl)benzene and (2,2'-bipyridyl)palladium(II) nitrate: synthesis and crystal structure.

The self-assembly of ditopic bis(1H-imidazol-1-yl)benzene ligands (L) and the complex (2,2'-bipyridyl-κN,N')bis(nitrato-κO)palladium(II) affords the supramolecular coordination complex tris[μ-bis(1H-imidazol-1-yl)benzene-κN:N]-triangulo-tris[(2,2'-bipyridyl-κN,N')palladium(II)] hexakis(hexafluoridophosphate) acetonitrile heptasolvate, [Pd(CHN)(CHN)](PF)·7CHCN, 2. The structure of 2 was characterized in acetonitrile-d by H/C NMR spectroscopy and a DOSY experiment. The trimeric nature of supramolecular coordination complex 2 in solution was ascertained by cold spray ionization mass spectrometry (CSI-MS) and confirmed in the solid state by X-ray structure analysis.

New polysubstituted monoterpenic thiazolidinones: synthesis, spectroscopic and crystal structure studies.

The synthesis of three new polysubstituted monoterpenic thiazolidin-4-ones, namely (Z)-3-methyl-2-{(E)-[(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene]hydrazinylidene}thiazolidin-4-one, CHNOS (2), (2Z,5Z)-5-[(dimethylamino)methylidene]-2-{(E)-[(1R,4R)-1,7,7-trimethylbicyclo[2.

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives.

Thermal decarbonylation of the acyl compounds [Mn(CO) (COR )] (R =CF , CHF , CH CF , CF CH ) yielded the corresponding alkyl derivatives [Mn(CO) (R )], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn( CO) (eq- CO)(R )] and [Mn( CO) (ax- CO)(R )] isotopomers and a ranking of the R donor power in the order CF View Article and Find Full Text PDF

A strongly fluorescent Ni complex with 2-(2-hy-droxy-eth-yl)pyridine ligands: synthesis, characterization and theoretical analysis and comparison with a related polymeric Cu complex.

The synthesis and characterization of di-aqua-bis-[2-(2-hy-droxy-eth-yl)pyridine-κ,)nickel(II) dinitrate, [Ni(CHNO)(HO)](NO), under ambient conditions is reported and compared with -poly[[bis-[2-(2-hy-droxy-eth-yl)pyridine-κ,]copper(II)]-μ-sulfato-κ:'], [Cu(CHNO)(SO)] [Zegh-ouan (2016 ▸). Private communication (refcode 1481676). CCDC, Cambridge, England].

The crystal structure of a new ferrocenyl P,N ligand: 1-[(2,2-di-methyl-hydrazin-1-yl-idene)meth-yl]-1'-(di-phenyl-phospho-rothio-yl)ferrocene.

The asymmetric unit of the title compound, [Fe(CHN)(CHPS)], contains two independent mol-ecules ( and ) with very similar conformations. Each mol-ecule is built up from a ferrocene unit substituted in the 1 and 1' positions by a protected sulfur di-phenyl-phosphine and by a di-methyl-hydrazine, -C(H)=N-N(CH), fragment. The two independent mol-ecules are linked by a C-H⋯N hydrogen bond.

Crystal structure of 2-isopropyl-4-meth-oxy-5-methyl-phenyl 4-methyl-benzene-sulfonate.

The title compound, CHOS, an hemisynthetic product, was obtained by the tosyl-ation reaction of the naturally occurring meroterpene -meth-oxy-thymol. The mol-ecule comprises a tetra-substitued phenyl ring linked to a toluene-sulfonate through one of its O atoms. In the crystal, C-H⋯O and C-H⋯π inter-actions link the mol-ecules, forming a three-dimensional network.

Synthesis of an Enantiomerically Pure Inherently Chiral Calix[4]Arene Phosphonic Acid and Its Evaluation as an Organocatalyst.

A facile method for the preparation of enantiomerically pure inherently chiral calix[4]arene phosphonic acid (cR,pR)-7 in four steps starting from the readily available and previously synthesized (cS)-enantiomer of calix[4]arene acetic acid 1 or its methyl ester 2 was developed. The first tests of this unique calixarene Brönsted acid with inherent chirality in organocatalysis of the aza-Diels-Alder reaction of imines with Danishefsky's diene and epoxide ring opening by benzoic acid were performed. The calixarene phosphonic acid (cR,pR)-7 shows good catalytic activities but with low enantioselectivities in these reactions.

Synthesis and Characterization of the Most Active Copper ATRP Catalyst Based on Tris[(4-dimethylaminopyridyl)methyl]amine.

The tris[(4-dimethylaminopyridyl)methyl]amine (TPMA) as a ligand for copper-catalyzed atom transfer radical polymerization (ATRP) is reported. In solution, the [Cu(TPMA)Br] complex shows fluxionality by variable-temperature NMR, indicating rapid ligand exchange. In the solid state, the [Cu(TPMA)Br][Br] complex exhibits a slightly distorted trigonal bipyramidal geometry (τ = 0.

Crystal structure, thermal and fluorescence properties of 2,2':6',2''-terpyridine-1,1',1''-triium tetra-chlorido-nickelate(II) chloride.

The title compound, (CHN)[NiCl]Cl, comprises an Ni cation tetra-hedrally coordinated by four chloride anions, a non-coordinating chloride anion and an essentially planar terpyridinium trication (tpyH), in which the central pyridinium ring forms dihedral angles of 5.7 (2) and 6.0 (2)° with the peripheral pyridinium rings.

Triangles and Squares for a Unique Molecular Crystal Structure: Unsupported Two-Coordinate Lithium Cations and CC Agostic Interactions in Cyclopropyllithium Derivatives.

Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl)cyclopropyllithium [{μ-c-C(SiMe )C H }Li] (1), synthesized by the reduction of 1-(phenylthio)-1-(trimethylsilyl)cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square.

Selective synthesis of (3-ferrocenylprop-2-en-1-yl)triphenylphosphonium iodide: crystal structure determination of two polymorphs.

This work is part of a project studying the reactivity of a new ferrocenyl allylammonium salt, [3-(trimethylazaniumyl)prop-1-en-1-yl]ferrocene iodide, (1)·I, with different nucleophiles. With nitrogen-based nucleophiles, different ferrocenyl allylamine isomers have been synthesized successfully in good yield. Optimization of the basicity of the reaction medium has allowed selection of the best operating conditions to obtain the targeted isomer.

Crystal and mol-ecular structure of (2,5)-3-(2-meth-oxy-phen-yl)-2-[(2-meth-oxy-phen-yl)imino]-5-(4-nitro-benzyl-idene)thia-zolidin-4-one.

In the title compound, CHNOS, the thia-zole ring (r.m.s.