Multiplurifunctionalized Phosphorus Dendrimers: Selective Functionalization of P(X)CL2 Terminal Groups

Abstract

Dendrimers are hyperbranched macromolecules constituted of repetitive branched units. They are synthesized step-by-step, a method which ensures a perfectly defined structure. This mini-review reports examples of rare “multiplurifunctionalized” dendrimers that have several types of functional groups precisely located on each terminal branching point. They are obtained thanks to the specificity of the reactivity of each Cl of P(X)Cl₂ (X = generally S, but also O) terminal groups on the surface of poly(phosphorhydrazone) dendrimers.     

Enantiospecific synthesis of the antituberculosis marine sponge metabolite (+)-puupehenone. The arenol oxidative activation route

[formula: see text] The total synthesis of the marine sesquiterpene quinone (+)-puupehenone, a promising new antituberculosis agent, was achieved in 10 steps starting from commercially available (+)-sclareolide. The key feature of this synthesis is the construction of the heterocycle via an intramolecular attack of the terpenoid-derived C-8 oxygen function onto an oxidatively activated 1,2-dihydroxyphenyl unit.     

A theoretical study of solvation energies of FCH2COO−, FCH2COOH,and F2CHCOO−

A continuum and a discrete-continuum models are used to determine the solvation energies of FCH₂COO^?, FCH₂COOH, and F₂CHCOO^?. For the anions, the continuum model provides results closer to the experiment, while for the acid, the addition of one water molecule improves the continuum-only energy.     

Ultrafast electron-phonon coupling in hollow gold nanospheres

Electronic energy relaxation in hollow gold nanospheres (HGNs) was studied using femtosecond time-resolved transient absorption spectroscopy. A range of HGNs having outer diameter-to-shell thickness aspect ratios of 3.5 to 9.5 were synthesized by a galvanic replacement method. The HGNs exhibited electron-phonon relaxation times that decreased from 1.18 ± 0.16 to 0.59 ± 0.08 ps as the aspect ratio increased over this range. The corresponding electron-phonon coupling constants, G, ranged from (1.67 ± 0.22) to (3.33 ± 0.45) × 10(16) W m(-3) K(-1). Electron-phonon coupling was also determined for solid gold nanospheres (SGNs) with diameters spanning 20 nm to 83 nm; no size dependence was observed for these structures. The HGNs with high aspect ratios exhibited larger electron-phonon coupling constants than the SGNs, whose average G value was (1.9 ± 0.2) × 10(16) W m(-3) K(-1). By comparison, low-aspect ratio HGNs exhibited values comparable to SGNs. The electron-phonon coupling of high-aspect ratio HGNs was also influenced by the surrounding fluid dielectric; slightly smaller G values were obtained when methanol was the solvent as opposed to water. This coupling enhancement observed for high-aspect ratio HGNs was attributed to the large surface to volume ratio of these structures, which results in non-negligible contributions from the environment.     

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P₆₆₆₁₄⁺) and tetrakis(pentafluorophenyl)borate anion (TB⁻) was employed within a water|P₆₆₆₁₄TB (w|P₆₆₆₁₄TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. ¹³⁷Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N′-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6 × 10¹¹ at the w|P₆₆₆₁₄TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ_α, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ_α of 2 and 8.2 × 10⁷, respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water–organic solvent mixture into an electron spray ionization mass spectrometer.     

Regioselective carbolithiation of o-amino-(E)-stilbenes: cascade route to the quinoline scaffold

[reaction: see text] The regioselective carbolithiation of substituted ortho-amino-(E)-stilbenes can be exploited to initiate cascade reaction sequences that can be utilized as new routes to substituted 3,4-dihydro-1H-quinolin-2-ones, 1,2,3,4-tetrahydroquinolines, 1,4-dihydroquinolines, and quinolines.     

Homophymine A, an anti-HIV cyclodepsipeptide from the sponge Homophymia sp

A new anti-HIV cyclodepsipeptide, homophymine A, was isolated from a New Caledonian collection of the marine sponge Homophymia sp. The structure of homophymine A was determined by interpretation of spectroscopic data, acid hydrolysis, and LC-MS analysis. Homophymine A contains 11 amino acid residues and an amide-linked 3-hydroxy-2,4,6-trimethyloctanoic acid moiety. Along with four D-, two L-, and one N-methyl amino acids, it also contains four unusual amino acid residues: (2S,3S,4R)-3,4-diMe-Gln, (2R,3R,4S)-4-amino-2,3-dihydroxy-1,7-heptandioic acid, L-ThrOMe, and (2R,3R,4R)-2-amino-3-hydroxy-4,5-dimethylhexanoic acid. In a cell-based XTT assay, homophymine A exhibited cytoprotective activity against HIV-1 infection with a IC50 of 75 nM.     

Beta-H transfer from the metallacyclobutane: a key step in the deactivation and byproduct formation for the well-defined silica-supported rhenium alkylidene alkene metathesis catalyst

The surface complex [([triple bond]SiO)Re([triple bond]CtBu)(=CHtBu)(CH2tBu)] (1) is a highly efficient propene metathesis catalyst with high initial activities and a good productivity. However, it undergoes a fast deactivation process with time on stream, which is first order in active sites and ethene. Noteworthy, 1-butene and pentenes, unexpected products in the metathesis of propene, are formed as primary products, in large amount relative to Re (>1 equiv/Re), showing that their formation is not associated with the formation of inactive species. DFT calculations on molecular model systems show that byproduct formation and deactivation start by a beta-H transfer trans to the weak sigma-donor ligand (siloxy) at the metallacyclobutane intermediate having a square-based pyramid geometry. This key step has an energy barrier slightly higher than that calculated for olefin metathesis. After beta-H transfer, the most accessible pathway is the insertion of ethene in the Re-H bond. The resulting pentacoordinated trisperhydrocarbyl complex rearranges via either (1) alpha-H abstraction yielding the unexpected 1-butene byproduct and the regeneration of the catalyst or (2) beta-H abstraction leading to degrafting. These deactivation and byproduct formation pathways are in full agreement with the experimental data.