Vinyl MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

Iterative cross-coupling represents a potentially general approach for the simple, efficient, and flexible construction of natural products, pharmaceuticals, and materials. N-Methyliminodiacetic acid (MIDA) boronates represent a promising platform for the development of this type of synthesis strategy. This report describes the discovery that vinyl MIDA boronate (1) is an air- and chromatographically stable compound that can be conveniently prepared on a multigram scale and serve as a versatile starting material for the preparation of a range of new MIDA boronate building blocks. Analogous to tert-butylethylene, 1 is also an excellent substrate for olefin cross-metathesis, providing access to a range of trans-alkenyl MIDA boronates as single stereoisomers. An improved synthesis of the very versatile bifunctional building block trans-(2-bromovinyl) MIDA boronate (2) is also described. Collectively, these results contribute to the expanding generality of the iterative cross-coupling approach.     

New trans–β–bergamotene derivatives in the root and the flower essential oils of Cyanthillium cinereum (L.) H. Rob. from Côte d’Ivoire

Root and flower essential oils of Cyanthillium cinereum (L.) H. Rob. (Synonym Vernonia cinerea (L.) Less.) (Asteraceae) collected in Southern Côte d’Ivoire was investigated using a combination of chromatographic and spectroscopic techniques. The root oil composition was dominated by trans–β–bergamotene (20.7%), β–elemene (19.0%), cyperene (10.6%), germacrene A (7.1%) and β–pinene (3.8%), whereas γ–humulene (31.0%), (E)–β–caryophyllene (17.0%), trans–β–bergamotene (7.7%), β–pinene (7.5%) and (E)–β–farnesene (6.0%) were the major components of flower oil. Two new compounds bearing the trans–β–bergamotene framework were identified: trans–β–bergamotenone and (E)–trans–β–bergamotenol.     

Characterization of a new epoxy-hydroxycarvotanacetone derivative from the leaf essential oil of Laggera pterodonta from Côte d’Ivoire

The leaf essential oil of Laggera pterodonta (DC.) Sch. Bip. ex Oliv. (Asteraceae) collected in the Eastern Côte d’Ivoire was investigated using a combination of chromatographic (GC-RI, CC, pc-GC) and spectroscopic (GC-MS, ¹³C NMR) techniques. Eighty-three components accounting for 98.0% of the whole composition were identified with 2,5-dimethoxy-p-cymene (43.3%), sabinene (14.1%), α-humulene (9.8%), (E)-β-caryophyllene (7.2%) and germacrene D (5.2%) as major compounds. This study led to the structural elucidation of a new natural compound, (3αH,4βH,6αH,1αMe)-1,6-epoxy-3-hydroxycarvotanacetone, angelic acid ester from the leaf oil by 1D and 2D NMR spectroscopy.     

Stress-induced crystal preferred orientation in the poromechanics of in-pore crystallization

A non-hydrostatic stress field affects the orientation of crystals growing in the pore network of an elastic porous medium. The hypothesis of a hydrostatic state of stress within the crystal has been implicitly made in the recent extension of poromechanics to in-pore crystalization (Coussy, 2006). This underlying hypothesis is revisited on a small-scale conceptual model based on Eshelby's problem and shows that chemo-mechanical equilibrium requires that the crystal adapts its shape and orientation to the far-field stress, therefore resulting at equilibrium in a hydrostatic state of stress within the crystal. The optimum crystal shape as a function of the far-field stress is consistently investigated, highlighting limiting cases. The small scale model allows to understand the macroscopic effects associated with deviatoric stresses in the poromechanics of in-pore crystallization. Moreover, it provides the building block for an up-scaling of the macroscopic tangent poroelastic properties, which depend on both the current crystal saturation and the state of stress. A dilute micromechanical scheme illustrates the variation of the macroscopic Biot's coefficient tensor as a function of deviatoric stresses. A simple configuration akin to a potential laboratory experiment finally illustrates the strong induced anisotropy of the crystallization induced macroscopic strain when deviatoric stresses are applied to the material prior to crystallization.     

Chemical Variability and In Vitro Anti-Inflammatory Activity of Leaf Essential Oil from Ivorian Isolona dewevrei (De Wild. & T. Durand) Engl. & Diels

The chemical variability and the in vitro anti-inflammatory activity of the leaf essential oil from Ivorian Isolona dewevrei were investigated for the first time. Forty-seven oil samples were analyzed using a combination of CC, GC(RI), GC-MS and ¹³C-NMR, thus leading to the identification of 113 constituents (90.8–98.9%). As the main components varied drastically from sample to sample, the 47 oil compositions were submitted to hierarchical cluster and principal components analyses. Three distinct groups, each divided into two subgroups, were evidenced. Subgroup I−A was dominated by (Z)-β-ocimene, β-eudesmol, germacrene D and (E)-β-ocimene, while (10βH)-1β,8β-oxido-cadina-4-ene, santalenone, trans-α-bergamotene and trans-β-bergamotene were the main compounds of Subgroup I−B. The prevalent constituents of Subgroup II−A were germacrene B, (E)-β-caryophyllene, (5αH,10βMe)-6,12-oxido-elema-1,3,6,11(12)-tetraene and γ-elemene. Subgroup II−B displayed germacrene B, germacrene D and (Z)-β-ocimene as the majority compounds. Germacrene D was the most abundant constituent of Group III, followed in Subgroup III−A by (E)-β-caryophyllene, (10βH)-1β,8β-oxido-cadina-4-ene, germacrene D-8-one, and then in Subgroup III−B by (Z)-β-ocimene and (E)-β-ocimene. The observed qualitative and quantitative chemical variability was probably due to combined factors, mostly phenology and season, then harvest site to a lesser extent. The lipoxygenase inhibition by a leaf oil sample was also evaluated. The oil IC₅₀ (0.020 ± 0.005 mg/mL) was slightly higher than the non-competitive lipoxygenase inhibitor NDGA IC₅₀ (0.013 ± 0.003 mg/mL), suggesting a significant in vitro anti-inflammatory potential.     

Neuropeltis acuminata (P. Beauv.): Investigation of the Chemical Variability and In Vitro Anti-inflammatory Activity of the Leaf Essential Oil from the Ivorian Species

The variability of chemical composition of the leaf essential oil (EO) from Neuropeltis acuminata, a climbing liana growing wild in Ivory Coast, was investigated for the first time. The in vitro anti-inflammatory activity was also evaluated. Thirty oil samples were isolated from leaves collected in three forests of the country and analyzed using a combination of Column Chromatography (CC), Gas Chromatography with Retention Indices (GC(FID)), Gas Chromatography-Mass Spectrometry (GC-MS), and ¹³Carbon-Nuclear Magnetic Resonance (¹³C-NMR). Fractionation by CC led to the first-time isolation from natural source of δ-cadinen-11-ol, whose structural elucidation by one dimension (1D) and 2D-NMR spectroscopy is reported here. Finally, 103 constituents accounting for 95.7 to 99.6% of the samples’ compositions were identified. As significant variations of the major constituents were observed, the 30 oil compositions were submitted to hierarchical cluster and principal components analyses. Five distinct groups were evidenced: Group I, dominated by (E)-β-caryophyllene, kessane, and δ-cadinene, while the main constituents of Group II were germacrene B, ledol, α-humulene, (E)-γ-bisabolen-12-ol, and γ-elemene. Group III exhibited guaiol, germacrene D, atractylone, (E)-γ-bisabolen-12-ol, δ-cadinene and bulnesol as main compounds. Group IV was dominated by (E)-nerolidol, guaiol, selina-4(15),7(11)-diene and bulnesol, whereas (E)-β-caryophyllene, α-humulene and α-muurolene were the prevalent compounds of Group V. As the harvest took place in the same dry season in the three forests, the observed chemical variability could be related to harvest sites, which includes climatic and pedologic factors, although genetic factors could not be excluded. The leaf oil sample S24 behaved as a high inhibitor of LipOXygenase (LOX) activity (half maximum Inhibitory Concentration, IC₅₀: 0.059 ± 0.001 mg mL⁻¹), suggesting an anti-inflammatory potential.     

First order rejection tests for multiple-objective optimization

Three rejection tests for multi-objective optimization problems based on first order optimality conditions are proposed. These tests can certify that a box does not contain any local minimizer, and thus it can be excluded from the search process. They generalize previously proposed rejection tests in several regards: Their scope include inequality and equality constrained smooth or nonsmooth multiple objective problems. Reported experiments show that they allow quite efficiently removing the cluster effect in mono-objective and multi-objective problems, which is one of the key issues in continuous global deterministic optimization.     

Resolution of chemical species in flow injection analysis by using self-modeling curve resolution

Mixtures can be resolved into their components by separation, spectrometric and kinetic (chemical) procedures, which have varying degrees of efficiency. Chemometric methods of data processing have proved useful for increasing resolution, especially in spectral and chromatographic procedures. This study shows that chemometric methods are also useful for kinetic flow-injection methods based on chemical reactions combined with multichannel spectral detection, where neither the reaction nor the detector provides adequate resolution. The problem of background absorbance of a sample in a flow-injection system with an ultraviolet/visible photodiode array detector is solved by applying a self-modeling curve resolution method. The example used is a mixture of methyl violet and phenolphthalein.