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.     

Use of weighted least-squares splines for calibration in analytical chemistry

Weighted least-squares spline functions are discussed and applied for calibration processes in analytical chemistry. Different weighting techniques are also considered, and for the evaluation of the results some quality coefficients are proposed. Depending upon the structure of the data, some weighting procedures may improve the results dramatically. Considering the results obtained in the case of TLC densitometry, it seems that nonlinear weighting procedures based upon the distance to the function are the best ones, with a plus for the y-distance type. It is difficult to give general rules regarding the optimal parameters of the weighted calibration splines-function order (m), number (N) and distribution of knots, and weighting technique. These depend upon the structure of the data. However, higher order splines are not recommended since the result might become extremely unstable. The example used to illustrate the performances of the procedures discussed here involved only a single independent variable. The method is general and extends practically to any number of variables, thus resulting in a multivariate approach.     

Synthesis of C-3' methyl taxotere (docetaxel)

Protected (3R,4S)-N-Boc-3-hydroxy-4-methyl-4-phenylazetidin-2-one has been synthesized stereoselectively and used to esterify protected 10-desacetylbaccatin III to give, following removal of the protecting groups, novel C-3' methyl taxotere (docetaxel).     

The reactant state for substrate-activated turnover of acetylthiocholine by butyrylcholinesterase is a tetrahedral intermediate

Secondary beta-deuterium kinetic isotope effects have been measured as a function of substrate concentration for recombinant human butyrylcholinesterase-catalyzed hydrolysis of acetyl-L3-thiocholine (L = 1H or 2H). The isotope effect on V/K is inverse, D3V/K = 0.93 +/- 0.03, which is consistent with conversion of the sp2 hybridized carbonyl carbon of the scissile ester bond of the E + A reactant state to a quasi-tetrahedral structure in the acylation transition state. In contrast, the isotope effect on Vmax under conditions of substrate activation is markedly normal, D3(betaVmax) = 1.29 +/- 0.06, an observation that is consistent with accumulation of a tetrahedral intermediate as the reactant state for catalytic turnover. Generally, tetrahedral intermediates for nonenzymatic ester hydrolyses are high-energy steady-state intermediates. Apparently, butyrylcholinesterase displays an unusual ability to stabilize such intermediates. Hence, the catalytic power of cholinesterases can largely be understood in terms of their ability to stabilize tetrahedral intermediates in the multistep reaction mechanism.     

A generalization of regula falsi

Summary The method of nondiscrete mathematical induction is applied to a multistep variant of the secant method. Optimal conditions for convergence as well as error estimates, sharp in every step, are obtained.     

Binuclear rhodium(II) complexes with leucine and proline

The dimeric rhodium(II) complexes [Rh₂(leu)₄(H₂O)₂]- (ClO₄)₄ and [Rh₂(pro)₄(H₂O)₂](ClO₄)₄ have been prepared and characterized by elemental analyses, i.r., u.v.–vis. and ¹H-n.m.r. spectroscopy. The amino acid molecules are coordinated as bridging ligands via their carboxylato groups. Cyclic voltammetry in DMF has shown that the complexes undergo a quasi-reversible reduction to yield dimers containing a Rh ₂ ³⁺ core. Oxidation processes within the 0–1.5V range were not observed.     

Heck reactions of aryl bromides with alk-1-en-3-ol derivatives catalysed by a tetraphosphine/palladium complex

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ efficiently catalyses the Heck reaction of alk-1-en-3-ol with a variety of aryl bromides. In the presence of hex-1-en-3-ol or oct-1-en-3-ol, the β-arylated carbonyl compounds were selectively obtained. Linalool and 2-methylbut-3-en-2-ol led to the corresponding 1-arylalk-1-en-3-ol derivatives. Turnover numbers up to 69,000 can be obtained for this reaction. A minor electronic effect of the substituents of the aryl bromide was observed. Similar reaction rates were observed in the presence of activated aryl bromides such as bromoacetophenone and deactivated aryl bromides such as bromoanisole.     

Shear-induced morphology transition and microphase separation in a lamellar phase doped with clay particles

We report on the influence of shear on a nonionic lamellar phase of tetraethyleneglycol monododecyl ether (C12E4) in D2O containing clay particles (Laponite RD). The system was studied by means of small-angle light scattering (SALS) and small-angle neutron scattering (SANS) under shear. The SANS experiments were conducted using a H2O/D2O mixture of the respective scattering length density to selectively match the clay scattering. The rheological properties show the familiar shear thickening regime associated with the formation of multilamellar vesicles (MLVs) and a shear thinning regime at higher stresses. The variation of viscosity is less pronounced as commonly observed. In the shear thinning regime, depolarized SALS reveals an unexpectedly strong variation of the MLV size. SANS experiments using the samples with lamellar contrast reveal a change in interlamellar spacing of up to 30% at stresses that lead to MLV formation. This change is much more pronounced than the change observed, when shear suppresses thermal bilayer undulations. Microphase separation occurs, and as a consequence, the lamellar spacing decreases drastically. The coincidence of the change in lamellar spacing and the onset of MLV formation is a strong indication for a morphology-driven microphase separation.     

First 13C‐NMR Assignments of Betaxanthins

Due to their inherent liability towards highly acidic conditions previously considered to be a prerequisite for data acquisition, betaxanthin structure dereplication by NMR spectroscopy has been scarcely reported and was, hitherto, exclusively based on ¹H‐NMR data interpretation. Applying only slightly acidic conditions, we herein report the first ¹³C‐NMR data of two betaxanthins, i.e., indicaxanthin ( 1 ), isolated from yellow‐orange cactus pear fruits (Opuntia ficus‐indica [L.] Mill . cv. ‘Gialla’), and of miraxanthin V ( 2 ) from yellow Swiss chard petioles (Beta vulgaris L. ssp. cicla [L.] Alef . cv. ‘Bright Lights’), as derived by gHSQC‐ and gHMQC‐NMR experiments and inverse detection.     

Synthèse des (−)-(6R)-et(+)-(6S)-tétrahydro-6-[(Z)-pent-2-ényl]-2H-pyran-2-one,lactones de Jasminum grandiflorum L. et de Polianthes tuberosa L.

Synthesis of (?)-(6R)- and (+)-(6S)-Tetrahydro-6-[(Z)-pent-2-enyl]-2H-Pyran-2-one, lactones from Jasminum grandiflorum L. and from Polianthes tuberosa L. (?)-(2S)-Ethyl 2-hydroxyhexanedioate ((2S)- 2 ) was obtained by kinetic resolution of racemic ethyl 2-hydroxy-hexanedioate with baker's yeast. The key intermediates (+)-(5R)- and (?)-(5S)-ethyl 5,6-epoxyhexanoate ((5R)- and (5S)- 6 , resp.) are proved to be useful synthons for the total synthesis of chiral 6-alkyl-δ-lactones, as exemplified by the preparation of both enantiomers of jasmine lactone ((6R)- and (6S)- 10 , resp.).