Directed Homogeneous Hydrogenation [New Synthetic Methods (65)]

Stereochemical control is a major concern in the application of homogeneous catalysis to organic chemistry. In this context, the directed hydrogenation of olefins employing cationic rhodium or iridium catalysts has considerable potential, for very high selectivity can be attained under mild reaction conditions. The only requirement is a polar functional group in proximity to the double-bond which remains bound to the metal during the catalytic cycle and thereby controls the Stereochemical course of hydrogen delivery through the constraints of chelation. The substituent is most frequently a hydroxy group OH but can also be an ester, amide or carbamate group; other groups remain to be scrutinized. In cyclic compounds, directed hydrogenation can lead to face-selectivity, and the polar substituent may be in the β-, γ-, or δ-position to the double-bond. Acyclic stereoselection ensues with β- or γ-substituents in appropriate compounds, and the configuration of reduced product is predictable on the basis of simple rules. The application of optically active rhodium complexes leads to useful kinetic resolution procedures.     

Some comments on modeling the linearized Boltzmann equation

Some exact solutions of the homogeneous and the inhomogeneous linearized Boltzmann equation (LBE) for rigid-sphere collisions are used to define two model equations in the general area of rarefied-gas dynamics. These equations are obtained from a systematic development of two synthetic scattering kernels that yield model equations that have as exact solutions certain known exact solutions of the homogeneous and of the inhomogeneous LBE. The first model established is defined in terms of the collisional invariants and the Chapman-Enskog integral equations for viscosity and for heat conduction. An extended model is defined also in terms of the collisional invariants and the Chapman-Enskog functions for viscosity and heat conduction, but the first and second Burnett functions are also included in the model. The variable collision frequency or generalized BGK model is also obtained as a special case. In addition, the exact mean-free paths defined, for rigid-sphere collisions and the LBE, in terms of viscosity or heat conduction are employed to define approximations of these quantities that are consistent with the use of the variable collision frequency model.     

咪唑环合成方法的新进展

综述了咪唑环合成方法的新进展，讨论了部分合成方法的特点及反应机理。参考文献４１篇。     

Template assembled synthetic proteins: Condensation of a multifunctional peptide to a topological template via chemoselective ligation

A chemoselective ligation via oxime bond formation is used for the chemical synthesis of template assembled peptides according to the TASP (Template Assembled Synthetic Proteins) approach. Aminooxyacetylation of the multifunctional partial sequence Lys- Arg- Asp- Ser of lactoferrin and subsequent condensation in aqueous solution with a topological template containing four selectively addressable aldehyde functions as attachment sites gives readily access to the TASP molecule.     

Chemistry of and with Highly Reactive Metals

Today, the synthetic chemist has a large repertoire of metal activation methods at his disposal. After a first breakthrough was made at the beginning of the seventies with the introduction of the Rieke metals, a series of further, in part more efficient methods were describes, based on which not only classical metal-induced reactions could be substantially improved but also completely new reactions could be discovered. In this article the individual activation methods are discussed and compared as far as is possible using the currently available data. Especially noteworthy are the metal–graphite combinations because of their unsurpassed reactivity and concomitant easy preparation and manipulation. As shown by numerous applications of these reagents on polyfunctional substrates, particularly natural products, high reactivity of the metal and excellent selectivity are by no means precluded. Besides the purely preparative aspects also insights gained so far into the general principles and limits of metal activation are outlined, and attempts at determining the morphology of highly dispersed systems are reported.     

Randomly censored partially linear single-index models

This paper proposes a method for estimation of a class of partially linear single-index models with randomly censored samples. The method provides a flexible way for modelling the association between a response and a set of predictor variables when the response variable is randomly censored. It presents a technique for “dimension reduction” in semiparametric censored regression models and generalizes the existing accelerated failure-time models for survival analysis. The estimation procedure involves three stages: first, transform the censored data into synthetic data or pseudo-responses unbiasedly; second, obtain quasi-likelihood estimates of the regression coefficients in both linear and single-index components by an iteratively algorithm; finally, estimate the unknown nonparametric regression function using techniques for univariate censored nonparametric regression. The estimators for the regression coefficients are shown to be jointly root-n consistent and asymptotically normal. In addition, the estimator for the unknown regression function is a local linear kernel regression estimator and can be estimated with the same efficiency as all the parameters are known. Monte Carlo simulations are conducted to illustrate the proposed methodology.     

A highly selective solid phase extraction sorbent for pre-concentration of sameridine made by molecular imprinting

Summary A novel approach to solid phase extraction, based on the use of a highly selective molecularly imprinted polymer, is presented. The versatility of this type of sorbent for solid phase extraction was demonstrated in a model batch-wise pre-concentration of sameridine prior to gas chromatography. Problems associated with leakage of remaining imprint molecules during the desorption phase could be eliminated by the use of a close structural analogue of sameridine as the imprint species. It was found that a major benefit of the imprinted polymer was its specificity, which lead to distinctly cleaner chromatographic traces and ability to improve sensitivity by extracting sameridine from larger sample volumes.     

Alkenylidenes in Organic Synthesis

Alkenylidenes R₂C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.     

The Photochemical Synthesis of Fine Chemicals with Sunlight

The light of the sun can be used directly for changing chemical structures photochemically. Any industrial application must conform to the limitations imposed by the spectral distribution of the photons from the sun, the interruptions to the radiation due to the day/night rhythm, and the weather. In this review, we describe the photochemical potential of the sun, give a fundamental treatment of the concept of photoreactors driven by sunlight (abbreviated to solar photoreactors), and give an account of the realization of this concept in the first pilot plant on the “Plataforma Solar de Almeria” in southern Spain and in other activities in this field. Based on experimental data from photochemical investigations on the pilot plant scale, possibilities, limitations, and the potential growth of solar photochemistry are described. Solar photochemistry, in our opinion, is a technique which could make a contribution to the chemistry of the future because of its photochemical synthesis potential, the avoidance of waste products, and the direct utilization of the sun, not only as a primary energy source, but also as a reaction partner.     

Anti-EPO and anti-NESP antibodies raised against synthetic peptides that reproduce the minimal amino acid sequence differences between EPO and NESP

Erythropoietin (EPO) is a hormone that regulates red blood cell production. Recombinant human EPO (rHuEPO) and NESP (novel erythropoiesis stimulating protein) have been produced for therapeutic purposes and also to improve sports performance. The primary sequences of rHuEPO and NESP differ by just five amino acids. Due to the high homology, no antibodies that are able to discriminate between both molecules have been obtained until now. The aim of the present work was to design synthetic peptides corresponding to the sequence that differs between EPO and NESP (87–90aa), that can then be used as immunogens to develop specific rabbit polyclonal antibodies for selectively detecting EPO and NESP. Three peptides were synthesized: EPO (81–95), NESP (81–95), and NESP (86–104), and these were coupled to KLH and OVA for immunization and screening purposes, respectively. The sera obtained were tested by ELISA on synthetic peptide–OVA conjugates and purified by immunoaffinity chromatography against the corresponding synthetic peptide. The specific purified antibodies were characterized by ELISA, SDS-PAGE, and isoelectric focusing, followed by western blot. Antisera raised against EPO (81–95) recognized rHuEPO but not NESP. In contrast, anti-NESP (84–106) sera gave a specific anti-NESP response only after immunoaffinity purification on a NESP (86–91) column. An efficient strategy for generating specific antibodies against EPO and NESP can be achieved by selecting suitable synthetic peptides. The antibodies obtained are able to differentiate between rHuEPO and NESP, and may be particularly useful for screening purposes in both therapeutic and antidoping contexts.