J. Appl. Cryst.の発刊に際して

This article sets out to review the chemistry relating to the synthesis of structural and functional analogues of the three classes of hydrogenases. This chemistry has grown explosively over the last 10 or so years since the first X-ray structures of [NiFe]- and [FeFe]-hydrogenase systems were published. There are now some 400 papers covering structural and functional aspects, with the majority of these associated with the di-iron system. As much emphasized in earlier papers

Structural and functional analogues of the active sites of the [Fe]-, [NiFe]-, and [FeFe]-hydrogenases.

Recent developments in the synthesis and utilization of chiral sulfoxides.

The palladium-catalyzed α-arylation of ketones has become a useful and general synthetic method. In this process, an enolate is generated from a ketone and base in the presence of an aryl halide, and a palladium catalyst couples this enolate with the aryl halide. With the advent of new catalysts composed of sterically hindered, electron-rich alkylphosphine and N-heterocyclic carbene ligands, this process now encompasses a broad range of enolates and related anions, including those derived from amides, esters, aldehydes, nitriles, malonates, cyanoesters, nitroalkanes, sulfones, and lactones. In the proposed mechanism for this reaction, the carbon−carbon bond of the product is formed by reductive elimination from an arylpalladium enolate intermediate. The structures and reactions of arylpalladium complexes of enolate, cyanoalkyl, and malonate ions have been studied to determine how the binding mode and electronic and steric parameters influence the rate and mechanism of reductive elimination.

Palladium-Catalyzed α-Arylation of Carbonyl Compounds and Nitriles

Additions to Metal-Activated Organonitriles†

Reaction of (R)-phenylglycinol with methyl 5-oxopentanoate gave either bicyclic lactam cis-1 (the kinetic product) or its isomer trans-1 (under equilibrating conditions) as the major products, which were converted to the corresponding (cis or trans) unsaturated lactams 4 and 5 On treatment with lithium alkyl (or aryl) cyanocuprates, these chiral building blocks undergo conjugate addition to give enantiopure trans-3,4-substituted 2-piperidone derivatives in high yield and stereoselectivity The synthetic potential of this transformation is illustrated by the synthesis of (+)-femoxetine and the two enantiomers of the known antidepressant paroxetine

Synthesis of Enantiopure trans-3,4-Disubstituted Piperidines. An Enantiodivergent Synthesis of (+)- and (−)-Paroxetine

Reactivity of [{M(C6F5)2(μ-OH)}2]2- (M = Pd or Pt) toward Aromatic Amines and Malononitrile

The co-ordinating properties of the ligand 3,5-bis(2-pyridyl)pyrazole (Hbpypz) are reported and complexes of general formulae [M(bpypz)]NO3·xH2O (M = CoII, NiII, CuII, ZnII, or CdII), [M(bpypz)] Cl·xH2O (M = MnII, CoII, NiII, or ZnII), and [M(bpypz)]Br·xH2O (M = CoII NiII or ZnII) are described. The crystal and molecular structure of [Ni2(bpypz)2(MeOH)4]Cl2·2H2O is also reported. The crystals are triclinic, space group P with a= 8.934(3), b= 8.958(6), c= 12.040(5)Aα= 72.02(3), β= 77.66(3), and γ= 68.58(3)°.

Notes. A planar, binucleating, pyrazole derivative ligand. Crystal structure of bis[µ-3,5-bis(2′-pyridyl)pyrazolato-N1N′:N2N″]-bis[dimethanolnickel(II)] dichloride dihydrate

The title carbonylative cycloaddition of five- to eight-member ring 3-halo- and 1-(halomethyl)cycloalkenes with different acetylenes was studied. From moderate to good yields of ring-fused and spiro cyclopentenone derivatives were obtained, especially in the reaction with acctylenes bearing electron-withdrawing substituents by propa selection of the reaction conditions to avoid the acetylene polyinsertion and/or other side reactions from the organonickel intamediates

Ring-fused and spiro cyclopentenones by Ni(CO)4-promoted intermolecular carbonylative cycloaddition of acetylenes with 3-halo- and 1-(halomethyl)cycloalkenes

Carles Miravitlles

Papers

Synthesis of Enantiopure trans-3,4-Disubstituted Piperidines. An Enantiodivergent Synthesis of (+)- and (−)-Paroxetine

Reactivity of [{M(C6F5)2(μ-OH)}2]2- (M = Pd or Pt) toward Aromatic Amines and Malononitrile

Notes. A planar, binucleating, pyrazole derivative ligand. Crystal structure of bis[µ-3,5-bis(2′-pyridyl)pyrazolato-N1N′:N2N″]-bis[dimethanolnickel(II)] dichloride dihydrate

Ring-fused and spiro cyclopentenones by Ni(CO)4-promoted intermolecular carbonylative cycloaddition of acetylenes with 3-halo- and 1-(halomethyl)cycloalkenes

Methionine and histidine Pd(II) and Pt(II) complexes: Crystal structures and spectroscopic properties