Asymmetric alkene epoxidation catalysed by a novel family of chiral metalloporphyrins: effect of structure on catalyst activity,stability and enantioselectivity

A selection of alkenes has been epoxidised with iodosylbenzene, catalysed by three related iron(III) tetraarylporphyrins: 1*, 2* and 3* with four 2,6-di(1-phenylbutoxy)phenyl groups, with one pentafluorophenyl and three 2,6-di(1-phenylbutoxy)phenyl groups and with two pentafluorophenyl and two 2,6-di(1-phenylbutoxy)phenyl groups, respectively. 1* is very sterically hindered and prone to self-oxidation which makes it a relatively poor epoxidation catalyst. Introducing the smaller pentafluorophenyl groups, in place of 2,6-di(1-phenylbutoxy)phenyl, increases catalyst reactivity, stability and selectivity. This change allows easier access of the substrates to the active oxidant and also, by decreasing the electron density on the porphyrin ligand, increases the reactivity of the oxoiron intermediate and its stability towards self-oxidation. A family of five homochiral catalysts, 1, 2 and 3, [the analogues of 1*, 2* and 3*, prepared from (R,R)-2,6-di(1-phenylbutoxy)benzaldehyde] and catalyst 4 with three pentafluorophenyl and one (R,R)-2,6-di(1-phenylbutoxy)phenyl group and 5 the manganese(III) analogue of 3 have been used to epoxidise three prochiral alkenes. All the reactions give low enantioselectivities. Using styrene as the substrate, (S)-styrene epoxide is the major enantiomer obtained with all the catalysts except 1 which leads to the (R)-styrene epoxide being preferred. In contrast cis-hept-2-ene and 2-methylbut-2-ene give the same major epoxide enantiomer with all the catalysts. The dependence of the ee values on catalyst and substrate structure, temperature and solvent is examined and discussed.     

On the Randomized Error of Polynomial Methods for Eigenvector and Eigenvalue Estimates

In this paper we consider the problem of estimating the largest eigenvalue and the corresponding eigenvector of a symmetric matrix. In particular, we consider iterative methods, such as the power method and the Lanczos method. These methods need a starting vector which is usually chosen randomly. We analyze the behavior of these methods when the initial vector is chosen with uniform distribution over the unitn-dimensional sphere. We extend and generalize the results reported earlier. In particular, we give upper and lower bounds on the _pnorm of the randomized error, and we improve previously known bounds with a detailed analysis of the role of the multiplicity of the largest eigenvalue.     

Stereoselective cyclopropanation of chiral 5-substituted dihydro-2H-piperazines

The Simmon–Smith cyclopropanation of enantiomerically enriched dehydropiperazines is reported. The reaction is highly stereoselective and allowed us to prepare new, enantiomerically enriched 3-substituted 2,5-diazabicyclo[4.1.0]heptane cores with high diastereomeric purity and a relative anti-configuration, which was assigned by NMR analysis.     

Synthesis of enantiomerically enriched amino sulfide building blocks from acyclic chiral amino allylsilanes

An efficient synthesis of various protected syn-β-sulfenyl amides is described. These are prepared from the corresponding enantiopure amino allylsilanes which are in turn obtained from naturally occurring amino acids. The key step for introduction of the sulfur substituent is a diastereoselective electrophilic sulfodesilylation which is carried out with phthalimidesulfenyl chloride. The resulting homochiral β-phthalimidesulfenyl amines with an allylic sulforated stereogenic center are useful building blocks, as they represent a starting point for subsequent functional manipulations.     

Superbase-promoted rearrangement of oxiranes to cyclopropanes

Aryl- and alkenyl substituted oxiranes, when submitted to treatment with superbasic reagents, undergo a highly regio- and stereoselective rearrangement leading to cyclopropylmethanol derivatives. The process can also be applied to mono- and dihydroxy substituted substrates thus leading to polyhydroxylated cyclopropanes.     

Vonnegut's spraying fountain—an oxygen-pressure dependent chemical process

Zusammenfassung Vonneguts klassisches Experiment über das Zerstäuben kleinster positiv hoch geladener Wassertröpfchen aus einer Kapillare wurde in einem geschlossenen Gefäss unter kontrollierten Bedingungen wiederholt. Die Zerstäubungsversuche wurden bei verschiedenen Mischungsverhältnissen des die Kapillare umgebenden Stickstoff-Sauerstoff-Gemisches ausgeführt, wobei Nebelproben gesammelt und analysiert wurden. Die erhaltenen Resultate deuten auf eine mögliche Reaktion des an der Kapillarenspitze in der Corona aktivierten Stickstoffes mit Wasser. Dies führt zur Bildung von Nitrit- und Nitrationen im gesammelten Nebel. In Gegenwart kleiner Sauerstoffmengen wird das Nitrit quantitativ zu Nitrat oxydiert. Dieses für die Atmosphärenchemie möglicherweise bedeutsame Phänomen ist begleicet von einer anderen Erscheinung, die vielleicht in Beziehung steht mit der Bildung natürlicher Nebel. Es wird gezeigt, dass bei schrittweiser Senkung des Sauerstoff-Stickstoff-Druckes in der Umgebung der Kapillare die Flüssigkeit nicht mehr zerstäubt wird, sondern als Strahl auftritt. Der den Übergang kennzeichnende Druck hängt direkt von der Zusammensetzung des Gasgemisches ab. Im reinen Stickstoff findet unterhalb 760 torr bei den gewählten experimentellen Bedingungen kein Zerstäuben statt, wogegen in einer Atmosphäre, deren Zusammensetzung der Luft entspricht, der Übergang bei etwa 615 torr liegt, also bei einem Druck der 1700 m Meereshöhe entspricht.     

Low‐Level Laser Therapy and Sodium Diclofenac in Acute Inflammatory Response Induced by Skeletal Muscle Trauma: Effects in Muscle Morphology and mRNA Gene Expression of Inflammatory Markers

Pharmacological therapy is widely used in the treatment of muscle injuries. On the other hand, low‐level laser therapy (LLLT) arises as a promising nonpharmacological treatment. The aim of this study was to analyze the effects of sodium diclofenac (topical application) and LLLT on morphological aspects and gene expression of biochemical inflammatory markers. We performed a single trauma in tibialis anterior muscle of rats. After 1 h, animals were treated with sodium diclofenac (11.6 mg g^‐1 of solution) or LLLT (810 nm; continuous mode; 100 mW; 3.57 W cm^?2; 1, 3 or 9 J; 10, 30 or 90 s). Histological analysis and quantification of gene expression (real‐time polymerase chain reaction—RT‐PCR) of cyclooxygenase 1 and 2 (COX‐1 and COX‐2) and tumor necrosis factor‐alpha (TNF‐α) were performed at 6, 12 and 24 h after trauma. LLLT with all doses improved morphological aspects of muscle tissue, showing better results than injury and diclofenac groups. All LLLT doses also decreased (P < 0.05) COX‐2 compared to injury group at all time points, and to diclofenac group at 24 h after trauma. In addition, LLLT decreased (P < 0.05) TNF‐α compared both to injury and diclofenac groups at all time points. LLLT mainly with dose of 9 J is better than topical application of diclofenac in acute inflammation after muscle trauma.     

Inversion of circulant matrices over

In this paper we consider the problem of inverting an circulant matrix with entries over . We show that the algorithm for inverting circulants, based on the reduction to diagonal form by means of FFT, has some drawbacks when working over . We present three different algorithms which do not use this approach. Our algorithms require different degrees of knowledge of and , and their costs range, roughly, from to operations over . Moreover, for each algorithm we give the cost in terms of bit operations. We also present an algorithm for the inversion of finitely generated bi-infinite Toeplitz matrices. The problems considered in this paper have applications to the theory of linear cellular automata.

     

An improved procedure for the preparation of the β-hydroxy-α-alkyl fatty acid fragment of mycolic acids

An approach to a β-hydroxy-α-alkyl fatty acid intermediate that can be applied in the synthesis of a range of mycolic acids is described.     

Colorimetric tools for solid-phase organic synthesis

One of the unresolved problems of solid-phase organic synthesis (SPOS) is the availability of general and rapid methods to monitor the transformation of functional groups present in molecules supported on insoluble supports. Color tests, far from providing the ultimate solution, may help in detection (and sometimes in quantification) of different functional groups. In this short review, we have collected most of the methods available and applied in SPOS with an Experimental Section that describes the procedure we have successfully applied to bead analyses in our laboratories.