The diazo route to diazonamide A: studies on the tyrosine-derived fragment

Various approaches to the tyrosine-derived fragment of the marine secondary metabolite diazonamide A are described. Initial efforts were focused on the originally proposed structure of the natural product, and a feasibility study established that a model 4-aryltryptamine could be readily prepared. Protected 4-bromotryptamine underwent Pd0-catalyzed coupling with the boronic acid derived from 2-bromophenyl allyl ether by Claisen rearrangement, O-methylation and lithiation-boration. The resulting biaryl was elaborated into an alpha-diazo-beta-ketoester, dirhodium(II)-catalyzed reaction of which with N-Z-valinamide gave the desired tryptamine-oxazole following cyclodehydration of the intermediate ketoamide. A potential precursor to the benzofuran ring of the original structure of diazonamide A was prepared in eight steps from N-Z-tyrosine tert-butyl ester. Iodination, O-protection and Stille coupling gave the cinnamyl alcohol 25, converted via the bromide into the allyl aryl ether 27. Subsequent Claisen rearrangement and oxidative cleavage of the alkene gave the lactol 29, converted into the desired benzofuranone 31. The revision in the structure of diazonamide A to 2 resulted in the targeting of an alternative tyrosine-derived model benzofuranone 41 synthesized in four steps from N-Z-tyrosine methyl ester 36 by a route involving Claisen rearrangement of cinnamyl ether 37. Poor yields in this sequence prompted an investigation into the intramolecular Heck reaction as a route to benzofuranone 50. Coupling of 3-iodotyrosine 44 with 2-phenylbutenoic acid 48 gave ester 49 that readily underwent intramolecular Heck reaction to give benzofuranone 50, albeit with poor stereocontrol.     

Dynamic Light Scattering and NMR Studies of Napin

We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of ¹H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated.     

Chloroplast Biogenesis 77: Two Novel Monovinyl and Divinyl Light-Dark Greening Groups of Plants and Their Relationship to the Chlorophyll a Biosynthetic Heterogeneity of Green Plants

Abstract— On the basis of the steady-state accumulation of divinyl (DV) or monovinyl (MV) protochlorophyllide (Pchlide) a in darkness (D) or in the light (L), green plants have been classified into three different greening groups namely dark divinyl-light divinyl (DDV-LDV), dark monovinyl-light divinyl (DMV-LDV) and dark monovinyl-light monovinyl (DMV-LMV) (Ionannides et al., Biochem. Syst. Ecol. 22, 211-220,1994). Interruption of the L phase of the photoperiod by a brief period of darkness (LD condition) revealed a predominance of different chlorophyll (Chl) a biosynthetic routes, depending upon the greening group affiliation of the plant species. For example, in DMV-LDV and DMV-LMV plants, the predominant Chl a biosynthetic routes under the LD condition appear to be the MV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Pchlide a. On the basis of DV and MV Pchlide a accumulation rates after re-darkening, this greening group is designated as a light-dark MV (LDMV) subgroup. In DDV-LDV plants, the predominant LD Chi a biosynthetic routes appear to be the DV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Chlide a. This greening group is designated as a light-dark DV (LDDV) subgroup. It is proposed that upon inhibiting the conversion of Pchlide a to Chi a by interruption of the L phase of the photoperiod by a brief period of D, the rates of DV and MV Pchlide a regeneration may reflect the carryover rates of DV and MV Pchlide a biosynthesis in L instead of reflecting a differential use of DV and MV carboxylic biosynthetic rates in D. It is also shown that in LDMV plants, MV Chlide a and MV Chi a are formed without the participation of [4-vinyl] Chlide a reductase. On the basis of recently published evidence, it is also argued that Pchlide oxidoreductase-A (POR-A) may be active in LDDV plants, while POR-B may predominate in LDMV plant species. The evolutionary significance of the LDDV and LDMV greening subgroups is discussed.     

Comparison of (π− d→nn withdσ(π+ d→pp) to test charge symmetry in the Δ-region

First results on ^– d are reported. The measurements were made using 8 specially designed neutron counters, which were carefully calibratedin situ. The differential cross sections atT =142, 180, 217, and 254 MeV were obtained at four angles between 0° and 90°, they are compared to ⁺ d pp data measured at the same energies and angles with the same setup. At every beam energy, the shape of the angular distributions of ^– d nn and ⁺ d pp is the same to ±2%. The absolute cross sections differ by 1 to 10%. The error in this comparison is ±4% implying a small violation of charge symmetry.Dedicated to Prof. I. laus on the occasion of his 60th birthdayDeceased     

Stereochemistry of cyclobutanone resulted from cycloadditions of t-butylcyanoketene to bicyclo[2.2.1]heptene derivatives, as evidence for a π2s+π2a reaction mode

The stereochemistry of the cyclobutanones 1-7, resulted from the reaction of t-butylcyanoketene with bicyclo[2.2.1]heptene, bicyclo[2.2.1]heptadiene, 1,4 - dihydro - 1,4 - methanonaphthalene, 1,4 - dihydro - 9 - (1 - methylethylidene) - 1,4 - methanonaphthalene, 1,4 - dihydro - 1,4 - epoxynaphthalene, l,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene (l,4,4a,8b) and 1,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene(1,4,4aβ,8bβ) was established as having the cyclobutanone ring exo and the t-Bu group in the configuration. These findings represent a stereochemical argument in favour of a _π2_s + _π2_a reaction mode of t-butylcyanoketene to the above mentioned bicyclo[2.2.1]heptene derivatives. Observations regarding preservation of the original configurations of alkenes as well as the geometrical distorsion of the cyclobutanones are shortly discussed.     

Dynamic kinetic resolution of transient hemiketals: a strategy for the desymmetrisation of prochiral oxetanols

Identification of an electron poor trifluoroacetophenone allows the formation of uniquely stable hemiketals from prochiral oxetanols. When exposed to a cobalt(ii) catalyst, efficient ring-opening to densely functionalized dioxolanes is observed. Mechanistic studies suggest an unprecedented redox process between the cobalt(ii) catalyst and the hemiketal that initiates the oxetane-opening. Based on this observation, a dynamic kinetic resolution of the transient hemiketals is explored that uses a Katsuki-type ligand for stereoinduction (up to 99 : 1 dr and 96 : 4 er) and allows a variety of 1,3-dioxolanes to be accessed (20 examples up to 98% yield).

Desymmetrization of prochiral oxetanols via an electron-deficient hemiketal intermediate is achieved. Key to this process is the catalyst''s chiral recognition of one of the two hemiketal enantiomers enabling an efficient dynamic kinetic resolution.     

Prediction of intracellular storage polymers using quantitative image analysis in enhanced biological phosphorus removal systems

The present study focuses on predicting the concentration of intracellular storage polymers in enhanced biological phosphorus removal (EBPR) systems. For that purpose, quantitative image analysis techniques were developed for determining the intracellular concentrations of PHA (PHB and PHV) with Nile blue and glycogen with aniline blue staining. Partial least squares (PLS) were used to predict the standard analytical values of these polymers by the proposed methodology. Identification of the aerobic and anaerobic stages proved to be crucial for improving the assessment of PHA, PHB and PHV intracellular concentrations. Current Nile blue based methodology can be seen as a feasible starting point for further enhancement. Glycogen detection based on the developed aniline blue staining methodology combined with the image analysis data proved to be a promising technique, toward the elimination of the need for analytical off-line measurements.     

Toward low‐noise synthetic turbulent inflow conditions for aeroacoustic calculations

The accuracy of boundary conditions for computational aeroacoustics is a well‐known challenge, due in part to the necessity of truncating the flow domain and replacing the analytical boundary conditions at infinity with numerical boundary conditions. In particular, the inflow boundary condition involving turbulent velocity or scalar fields is likely to introduce spurious waves into the domain, therefore degrading the flow behavior and deteriorating the physical acoustic waves. In this work, a method to generate low‐noise, divergence‐free, synthetic turbulence for inflow boundary conditions is proposed. It relies on the classical view of turbulence as a superposition of random eddies convected with the mean flow. Within the proposed model, the vector potential and the requirement that the individual eddies must satisfy the linearized momentum equations about the mean flow are used. The model is tested using isolated eddies convected through the inflow boundary and an experimental benchmark data for spatially decaying isotropic turbulence. Copyright © 2013 John Wiley & Sons, Ltd.