Total synthesis of indole and dihydroindole alkaloids. VI. The total synthesis of some monomeric vinca alkaloids: dl-vincadine, dl-vincaminoreine, dl-vincaminorine, dl-vincadifformine, dl-minovine and dl-vincaminoridine.

A synthetic approach to a variety of monomeric Vinca alkaloids is described. The sequence involves, among its crucial phases, the generation of appropriate nine-membered ring intermediates which are then elaborated via a transannular cyclization approach to the desired natural products.     

Bioinspired Artificial Photosynthetic Systems

Mimicking photosynthesis using artificial systems, as a means for solar energy conversion and green fuel generation, is one of the holy grails of modern science. This perspective presents recent advances towards developing artificial photosynthetic systems. In one approach, native photosystems are interfaced with electrodes to yield photobioelectrochemical cells that transform light energy into electrical power. This is exemplified by interfacing photosystem I (PSI) and photosystem II (PSII) as an electrically contacted assembly mimicking the native Z-scheme, and by the assembly of an electrically wired PSI/glucose oxidase biocatalytic conjugate on an electrode support. Illumination of the functionalized electrodes led to light-induced generation of electrical power, or to the generation of photocurrents using glucose as the fuel. The second approach introduces supramolecular photosensitizer nucleic acid/electron acceptor complexes as functional modules for effective photoinduced electron transfer stimulating the subsequent biocatalyzed generation of NADPH or the Pt-nanoparticle-catalyzed evolution of molecular hydrogen. Application of the DNA machineries for scaling-up the photosystems is demonstrated. A third approach presents the integration of artificial photosynthetic modules into dynamic nucleic acid networks undergoing reversible reconfiguration or dissipative transient operation in the presence of auxiliary triggers. Control over photoinduced electron transfer reactions and photosynthetic transformations by means of the dynamic networks is demonstrated.     

Antenna-functionalized dendritic β-diketonates and europium complexes: synthetic approaches to generation growth

Six dendritic β-diketonates and their corresponding europium complexes were synthesized. These dendritic β-diketonate ligands consist of dibenzoylmethane cores, Fréchet-type poly(aryl ether) dendrons, and the carbazole-grafted peripheral functional groups. The designs of dendrimers are on the basis of high light-harvesting capability and dendron functionalization in virtue of the high extinction coefficient and carrier-injection adjustment of carbazole units. Different approaches to generation growth were utilized: the first generation europium complexes through etheral connectivity were developed via convergent synthetic approach; the second and third generation dendrons through esteral connectivity were developed by a hyperbranch core approach containing the advantages of convergent and divergent approaches. Their chemical structures were well characterized. Preliminary results show that the dendron-functionalized carbazole units not only tune the carrier-transporting capability, but also exhibit strong light-harvesting potential, resulting in a strong intense emission from the central Eu(III) ion via sensitization.     

A versatile approach to hybrid thiadiazine-based molecules by the Ugi four-component reaction

Aiming at developing a versatile method for the generation of hybrid heterocyclic molecules, we describe a sequential approach comprising the formation of carboxy-functionalized 1,3,5-thiadiazines followed by the Ugi reaction with variation of the amino and the isonitrile components. The method enables the generation of structurally diverse molecular hybrids including peptide, lipid, steroidal and sugar moieties linked to the 1,3,5-thiadiazine scaffold.     

An approach for disaccharide chiron synthesis using a Ferrier-type rearrangement

We report a new approach for the synthesis of new chiral synthons in which two unsaturated sugars are linked via a glycosidic bond. The di-unsaturated disaccharide can be further functionalized using effective, highly selective methods and used in convergent syntheses of relatively complex glycoconjugates. Our approach utilizes in situ generation of active glycosyl donors via Ferrier-type rearrangement under phase-transfer conditions and subsequent reaction with a nucleophile.     

Increasing the signal to noise ratio in amperometry and polarography using the controlled-growth mercury drop electrode

A new approach to current sampling in amperometric and polarographic measurement is described. This approach requires the application of a step-by-step mode of mercury drop generation. The advantages are: (1) in amperometric measurements an increase of the signal to noise ratio; (2) in polarographic measurements and computer aided experiments the noise level can be markedly reduced.     

Single cyclized molecule structures from RAFT homopolymerization of multi-vinyl monomers

We explore a kinetically controlled strategy to suppress the gelation in the homopolymerization of multi-vinyl monomers (MVMs) via RAFT polymerization. We report the generation of 3D single cyclized polymer structures from the RAFT process, which significantly contradicts the classic F-S theory. This approach enables synthesis of a new generation of nanosize macromolecular architectures.     

Contraction operator over electronic fock space. II. Weak representability problem

Two approaches in treating the weak representability problem for density operators are studied. In the first approach this problem is reduced to the minimization of a certain distance function. The second approach is based on inductive generation of linear inequalities for diagonal elements of the second-order density operators. Generalization of Kuhn–Yoseloff's results is also discussed.     

Modular solid-phase synthetic approach to optimize structural and electronic properties of oligoboronic acid receptors and sensors for the aqueous recognition of oligosaccharides

This article describes the design and optimization of the first entirely modular, parallel solid-phase synthetic approach for the generation of well-defined polyamine oligoboronic acid receptors and fluorescence sensors for complex oligosaccharides. The synthetic approach allows an effective building of the receptor polyamine backbone, followed by the controlled diversification of the amine benzylic side chains. This approach enabled the testing, in a modular fashion, of the effect of different arylboronic acid units substituted with unencumbering para electron-withdrawing or electron-donating groups. The feasibility of this approach toward automated synthesis was also investigated with the assembly of a sublibrary of receptors by means of the Irori MiniKan technology. Several sublibraries of anthracene-capped sensors containing two or three arylboronic acids were synthesized, and their binding to a series of model disaccharides was examined in neutral aqueous media. The calculation of association constants by fluorescence titrations confirmed that subtle changes in the structures of the interamine spacers in the polyamine backbone can have a significant effect on the stability of the resulting complexes. Most importantly, this study led to the determination of the preferred electronic characteristics for the arylboronate units, and suggests that a new generation of receptors containing very electron-poor arylboronic acids could lead to a significant improvement of binding affinities.     

Microwave-assisted synthesis of 3-aryl-pyrimido[5,4-e][1,2,4]triazine-5,7(1H,6H)-dione libraries: derivatives of toxoflavin

The parallel synthesis of a library of toxoflavin derivatives is described. The microwave-assisted approach involves the de novo generation of the heterocyclic scaffold and allows for facile introduction of a variety of fragments.     

Modular Columnar Supramolecular Polymers as Scaffolds for Biomedical Applications

Self‐assembly of discotic molecules into supramolecular polymers offers a flexible approach for the generation of multicomponent one‐dimensional columnar architectures with tuneable biomedical properties. Decoration with ligands induces specific binding of the self‐assembled scaffold to biological targets. The modular design allows the easy co‐assembly of different discotics for the generation of probes for targeted imaging and cellular targeting with adjustable ligand density and composition.     

(+)-Phorboxazole A synthetic studies. A highly convergent, second generation total synthesis of (+)-phorboxazole A

[structure: see text] A second generation total synthesis of the potent antitumor agent (+)-phorboxazole A (1) has been achieved. The cornerstone of this approach comprises a more convergent strategy, involving late-stage Stille union of a fully elaborated C(1-28) macrocycle with a C(29-46) side chain. The second generation synthesis entails the longest linear sequence of 24 steps, with an overall yield of 4.2%.     

Efficient generation of configuration interaction matrix elements

A method for the efficient generation of CI matrix elements over spin eigenfunctions is presented. Practical application of the approach is limited to configurations with about 10 open shells, but the algorithm results in the generation of more than 2200 matrix elements/second on an IBM 370/158 computer including all overhead for a large matrix which contains 50% non-zero elements.     

Synthesis,characterization, and application of melamine‐based dendrimers supported on silica gel

Dendrimers based on melamine have been covalently attached to silica gel with convergent and divergent approaches. These approaches yield different products. Each step of the synthesis can be monitored with Fourier transform infrared spectroscopy, thermal gravimetric analysis, and X‐ray photoelectron spectroscopy. The organic molecules can be isolated by chemical etching the organosilica material with HF and then analyzed by mass spectrometry. The convergent approach, which relies on the solution‐phase synthesis of the dendrimer before its attachment onto silica gel, produces materials that are ～20% w/w organic regardless of the generation of the dendrimer used in the preparation of these composites and without apparent defects in the dendrimer structure. Materials prepared with the divergent approach show increasing percentages of organic material with each generation, but the dendrimers show structural defects including incomplete branching. In a survey of sequestration potential, materials obtained with the divergent approach removed more atrazine from solution than the more homogeneous materials obtained from the convergent approach. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 168–177, 2005     

Biomimetic total synthesis and antimicrobial evaluation of anachelin H

The first biomimetic total synthesis of the iron chelator anachelin H isolated from the cyanobacterium Anabaena cylindrica is reported. A first generation approach delivered one enantiomeric series of the polyketide fragment. Comparison of the 1H NMR data suggested the relative configuration of this anachelin fragment. The relative and absolute configuration of anachelin H was then established by total synthesis. A second generation approach involved the enzymatic conversion of N,N-dimethyltyramine to the anachelin chromophore. It was demonstrated that the enzyme tyrosinase is activated by the product during this reaction, the anachelin chromophore can serve as a tyrosinase activator. Anachelin H was evaluated against a panel of eleven bacterial and fungal pathogens, and moderate antibiotic activity (32 microg/mL) against Moraxella catarrhalis was found.     

Direct metalation of methoxymethyl arylmethyl ethers: A tin-free approach to the generation of α-alkoxyalkoxy-substituted aryllithiums

The generation of a series of α-methoxymethoxy-substituted arylmethyllithiums was achieved by direct metalation of the corresponding arylmethyl methoxymethyl ethers. While the effect of substituents at the benzylic position is straightforward, substituents located on the aromatic ring promote the set up of a competition between lateral and aromatic metalation, strongly affected by the position and relative ortho directing properties of the new substituent. The proposed methodology allows a simple approach to the generation of a wide array of functionalized organolithium reagents.     

Catalytic Enantioselective CH Functionalization of Alcohols by Redox‐Triggered Carbonyl Addition: Borrowing Hydrogen,Returning Carbon

The use of alcohols and unsaturated reactants for the redox‐triggered generation of nucleophile–electrophile pairs represents a broad, new approach to carbonyl addition chemistry. Discrete redox manipulations that are often required for the generation of carbonyl electrophiles and premetalated carbon‐centered nucleophiles are thus avoided. Based on this concept, a broad, new family of enantioselective C? C coupling reactions that are catalyzed by iridium or ruthenium complexes have been developed, which are summarized in this Minireview.     

Oligosaccharide-modified poly(propyleneimine) dendrimers: synthesis, structure determination, and Cu(II) complexation

The multiple application of reductive amination on primary amino groups of first and second generation poly(propyleneimine) dendrimers is used as a one-pot approach to introduce twice the amount of the oligosaccharide units as surface groups, compared to initially present amino groups in the first and second generation dendrimers. This was proven by (1)H NMR, MALDI-TOF-MS, and LILBID-MS analysis. The size of these dendrimers was determined by the hydrodynamic radius using pulsed field gradient NMR and dynamic light scattering. Molecular modeling confirmed the presence of dense-shell dendrimers. These dendrimers exhibit a generation dependent Cu(II)/dendrimer ratio in an aqueous environment, highlighting these materials as possible metal-carrier systems with a well-defined oligosaccharide protection shell for application in a biological environment.     

Solid phase peptide templated glycosidic bond formation

Glycosylation reactions performed between a glycosyl donor and acceptor covalently linked to a peptide template both in the solution and solid phase give similar yields and product distributions. The adoption of a solid phase approach opens the way for the synthesis of libraries of peptide templates in an attempt to screen for particular peptide sequences that effect complete regio-and stereochemical control during glycosidic bond formation, whilst the use of second generation donors allows the possibility of an iterative approach.