Direct Synthesis of Saturated Alcohols from Conjugated Ketones Using NaBH and Catalytic Amount of CuCN in Ethanol: Additive Catalysis with a Lithium Salt or a Sodium Salt.

A direct, efficient, and highly chemoselective synthesis of saturated alcohols through one-pot sequential 1,4- and 1,2-reduction of cyclic and acyclic conjugated ketones is reported. The saturated alcohols are obtained in very good yields using sodium borohydride (NaBH) as a reducing agent and a catalytic amount of copper(I) cyanide (CuCN) in ethanol as a green solvent. This nontoxic solvent significantly favors full 1,4-reduction, as opposed to methanol.

Novel Synthesis of IMC-48 and Affinity Evaluation with Different i-Motif DNA Sequences.

During the last decade, the evidence for the biological relevance of i-motif DNA (i-DNA) has been accumulated. However, relatively few molecules were reported to interact with i-DNA, and a controversy concerning their binding mode, affinity, and selectivity persists in the literature. In this context, the cholestane derivative has been reported to modulate gene expression by stabilizing an i-motif structure in its promoter.

Electronic Structure and Reactivity of One-Electron-Oxidized Copper(II) Bis(phenolate)-Dipyrrin Complexes.

The sterically hindered bis(phenol)-dipyrrin ligands LH and LH were reacted with 1 equiv of copper(II) under ambient conditions to produce the copper radical complexes [Cu(L)] and [Cu(L)]. Their X-ray crystal structures show relatively short C-O bond distances (mean bond distances of 1.287 and 1.

A Structurally Characterized Cu Complex Supported by a Bis(anilido) Ligand and Its Oxidative Catalytic Activity.

Three copper(II) complexes of the (R,R)-N,N'-bis(3,5-di-tert-butyl-2-aminobenzylidene)-1,2-diaminocyclohexane ligand, namely [Cu( L)], [Cu( LH)] and [Cu( LH )] , were prepared and structurally characterized. In [Cu( LH )] the copper ion lies in an octahedral geometry with the aniline groups coordinated in equatorial positions. In [Cu( L)] the anilines are deprotonated (anilido moieties) and coordinated to an almost square-planar metal ion.

Fast racemisation of chiral amines and alcohols by using cationic half-sandwich ruthena- and iridacycle catalysts.

The lipase-catalysed resolution of alcohols and amines yields only 50 % of the desired enantiopure product. However, addition of a racemisation catalyst leads to 100 % yield in what is called a dynamic kinetic resolution (DKR). There is a need for new racemisation catalysts that are fast and compatible with the conditions of the enzymatic reaction.

Catalytic direct-type substitution reaction of alpha-alkyl enolates: a Pd/Brønsted base-catalysed approach to the decarboxylative allylation of sulfonylimidates.

A mild and efficient process for the direct-type catalytic allylation of sulfonylimidates has been developed; this reaction represents the first example of Brønsted base-catalysed, in situ generation and use of alpha-alkyl enolates in substitution reactions; the success of this methodology stems from the tunable alpha-proton acidity and nucleophilicity of sulfonylimidates, which could be harnessed in the realization of a broader range of catalytic direct-type reactions using ester equivalents as nucleophiles.

Dynamic kinetic resolution of racemic beta-haloalcohols: direct access to enantioenriched epoxides.

The direct chemo-enzymatic DKR of racemic beta-haloalcohols is reported, yielding the corresponding optically active epoxides in a single step. The mutant haloalcohol dehalogenase HheC Cys153Ser Trp249Phe is used for the asymmetric ring closure, whereas racemization of the remaining enantiomer of the haloalcohol is achieved using the new iridacycle 3, one of the most effective racemization catalysts to date for beta-haloalcohols.

Palladium-tetraphosphine complex: an efficient catalyst for the coupling of aryl halides with alkynes.

The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 system catalyses the coupling of aryl halides with alkynes with very high ratios of substrates-catalyst in good yields; a turnover number of 2600000 can be obtained for the reaction of 4-trifluoromethylbromobenzene with phenylacetylene in the presence of this catalyst.