New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

A simple and green procedure for the conjugate addition of thiols to conjugated alkenes employing polyethylene glycol (PEG) as an efficient recyclable medium

Polyethylene glycol (PEG) is found to be an inexpensive, nontoxic, environmentally friendly reaction medium for the conjugate addition of thiols to conjugated alkenes to afford the corresponding adducts in excellent yields under mild and neutral conditions. Products of undesirable side reactions resulting from polymerization are not observed. The use of PEG avoids the use of either acid or base catalysts for this conversion and moreover PEG can be recovered and reused.     

Synthesis and use of chiral substituted benzenes containing 1,2-diols protected as cyclic acetals

1,2-Dihydroxy benzenes have been protected as cyclic diacetals using 2,3-butane dione. These diacetals are extremely robust and can be further chemically diversified and resolved with chirality embedded in the 1,4-dioxane ring attached to the aromatic back bone as a result of the anomeric effect. These systems can serve as ligands, auxiliaries or organocatalysts for asymmetric synthesis.     

L‐Proline–H2O2: A New Chemoselective Approach for Oxidation of Sulfides to Sulfoxides

A facile and selective oxidation of sulfides to sulfoxides using an L‐proline–H₂O₂ system for structurally divergent sulfide substrates with excellent yields at ambient conditions is reported.     

Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Validated ultra-performance liquid chromatography tandem mass spectrometry method for the determination of pramipexole in human plasma

A sensitive and high throughput ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS-MS) method has been developed for the determination of pramipexole, a dopamine agonist, in human plasma. Sample preparation involved liquid-liquid extraction of pramipexole and ranitidine as the internal standard (IS) in ethyl acetate from 100 μL human plasma. The chromatographic separation is achieved on a Waters Acquity UPLC BEH C18 (100 mm × 2.1 mm, 1.7 μm) analytical column using an isocratic mobile phase, consisting of 10 mM ammonium formate (pH 7.50)-acetonitrile (15:85, v/v), at a flow-rate of 0.5 mL/min. The precursor → product ion transition for pramipexole (m/z 212.1 → 153.0) and IS (m/z 315.0 → 176.1) were monitored on a triple quadrupole mass spectrometer, operating in the multiple reaction monitoring (MRM) and positive ion mode. The method was validated over a wide dynamic concentration range of 20-4020 pg/mL. Matrix effect is assessed by post-column infusion experiment and the process efficiency were 91.9% and 85.7% for pramipexole and IS, respectively. The method is rugged and rapid with a total run time of 1.5 min and is applied to a bioequivalence study of 0.25 mg PPX tablet formulation in 30 healthy Indian male subjects under fasting condition.     

New substituted 2-aminomethyl-2-oxo-2λ5-perhydro-[1,3,2]oxazaphospholo [3,4-a]pyridine: Design,synthesis and antimicrobial activity

The synthesis of a new series of P-heterocyclic compounds, substituted 2-aminomethyl-2-oxo-2λ⁵-perhydro-[1,3,2]oxazaphospholo[3,4-a]pyridine derivatives 8(a-j), was accomplished. A key intermediate, 2-(chloromethyl)-2-oxo-2λ⁵-perhydro-[1,3,2]oxazaphospholo[3,4-a]pyridine (6) was primarily synthesized by the condensation of (±)-2-piperidinemethanol (4) and chloromethylphosphonic dichloride (5); subsequently, it was treated with various heterocyclic amines/benzylamines/aminoacid esters, 7(a-j) to obtain the desired products. The structures of the newly synthesized compounds were elucidated by ¹H, ¹³C, and ³¹P NMR spectroscopy, mass spectra and elemental analyses. The biological potency of title products was investigated by screening in vitro antimicrobial activity. The bio-screening data revealed that most of the synthesized derivatives showed potent growth of inhibition against fungi while compared with bacteria. Particularly, compounds 8c and 8i against bacterial strains, and 8a and 8f against fungi exhibited promising activity.     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Ozone initiated oxidation of long chained n -alkanes in the presence of activated charcoal or silica gel

Photolysis behavior of acetamiprid in different kinds of surfactant solutions were investigated. The results showed that acetamiprid was prone to photolysis when exposed to the irradiation of a mercury lamp, and the photolysis kinetics fit in well with the first-order kinetic equation. Surfactants did not participate in the acetamiprid’s photolysis process directly, whereas they all had obvious inhibiting effects on it.