The observation of an oxaphosphetane intermediate in the phosphonate modification of the wittig oelfin synthesis

A signal at high field is observed in the ³¹P nmr of the reaction mixtures of some ketones with a five-membered cyclic phosphonate.     

Investigation of Reaction Mechanism of Amino Acids and Phosphorus Trichloride by 31P NMR and ESI‐MS/MS

The reaction of amino acids and phosphorus trichloride in THF was studied by ³¹P NMR tracing and ESI‐MS/MS. A series of hydridophoranes and cyclic dipeptides were obtained. The reaction presented interesting diversity and the reaction mechanism was proposed. The mechanism suggests that phosphorus plays an important role in the synthesis of amino acid hydridophorane and cyclic dipeptides. The results also show that ³¹P NMR and ESI‐MS/MS are useful tools for the investigation of reaction mechanism.     

Gold(I)‐Catalyzed Divergence in the Preparation of Bicyclic Enol Esters: From Exclusively [3C+2C]‐Cycloaddition Reactions to Exclusive Formation of Vinylcyclopropanes

With the use of benzonitrile‐stabilized Au^I catalyst [Au(IPr)(NCPh)]SbF₆ ( Ic ; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), a spectrum of reactivity is observed for propargyl ester 4 a with cyclic vinyl ethers, ranging from exclusively [3C+2C] cycloaddition reactions to exclusively cyclopropanation depending only on the structure of the substrate. Some initially formed cyclopropanation products rearrange into the corresponding formally [3C+2C] cycloaddition products after treatment with fresh Au^I complex at 80 °C. Vinylcyclopropanes formed from dihydrofuran and dihydropyran resisted such rearrangement, even in the presence of fresh Au^I catalyst at elevated temperature. This study addresses an important mechanistic question concerning whether the five‐membered‐ring products were produced by a direct [3C+2C] cycloaddition reaction or by a sequential cyclopropanation/ring‐expansion reaction. A dual pathway is proposed for the Au^I‐catalyzed reactions between propargyl esters and cyclic vinyl ethers. The different behavior among vinyl cyclic ethers is attributed to the difference in the polarization of the π bond. Highly polarized bonds appear to undergo the cycloaddition reaction whereas less polar π‐bonds produce cyclopropanes.     

Formation of Active Cyclic Five-membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

The cyclic five-membered frustrated phosphane/borane Lewis pairs 11 a , b featuring the bulky octaethylhydrindacenyl- (Eind) substituent or its mono-bromo derivative (^BrEind) at phosphorus are monomeric at room temperature. The reactive frustrated Lewis pairs (FLPs) cleave dihydrogen. The cyclic FLP 11 b (^BrEind) undergoes 1,2-P/B addition to ethylene to give the zwitterionic heteronorbornane derivative 14 b . It reacts similarly with the carbon–carbon double bond of norbornene. With a variety of organic π-reagents, the cyclic FLP 11 b often undergoes reaction sequences reminiscent of the Alder–Rickert reaction: the cycloaddition reaction is followed by rapid cycloreversion to form new five-membered heterocyclic FLP products with extrusion of ethene. Reactions of 11 b with benzaldehyde or with acetylenes follow this reaction pattern.     

Amination of quinolones with morpholine derivatives

The aromatic nucleophilic substitution reaction of 7-chloroquinolone carboxylic acid and its ethyl ester with cyclic amines under microwave irradiation conditions was investigated. ¹H NMR spectroscopy was used to monitor the progress of the substitution reaction. The reaction proceeded in high yield with simple cyclic amines and was less efficient for sterically more demanding bimorpholine derivatives. A Pd-catalyzed amination of quinolone carboxylic acid ethyl ester with bimorpholine derivatives provided new C-7 bimorpholino-substituted quinolone derivatives.     

Interfacial electrochemistry of hypophyseal polypeptide hormones

The adsorption and the electrode reaction of the cyclic polypeptide hormones oxytocin, desamino-oxytocin and vasopressin at the mercury/water interface was investigated by a.c. and d.c. polarography and by cyclic voltammetry. The saturation surface concentrations as obtained by the different methods under different potential oscillations, and at two pH values (2 and 6.6) varied between 3 × 10¹³ and 5 × 10¹³ molecules cm^-2. The kinetics of the adsorption—desorption reaction and of the electrode process was in every case the slowest for the non-charged desamino-oxytocin. Vasopressin behaved the most reversibly in a.c. polarography, while oxytocin showed the most reversible behavior in cyclic voltammetry. The difference in behavior is related to the difference in charge and hydrophobicity of the different polypeptides, affecting adsorption interactions and the catalytic reaction with the mercury surface.     

Direct Synthesis of High Purity Silicon Wires by Electrorefining in Molten KF-NaF Eutectic

The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 oC using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si⁴⁺. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si⁴⁺→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.     

Synthesis and ring‐opening polymerization of macrocyclic aryl ketone oligomers

A series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge‐linking electron‐rich aromatic hydrocarbons 3a–d under pseudo‐high dilution conditions in the presence of Lewis base via Friedel–Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI‐TOF‐MS, GPC, and ¹H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring‐opening polymerization in the melt by using potassium 4,4′‐biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring‐opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa · S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring‐opening polymerization. Copyright © 2009 John Wiley & Sons, Ltd.     

A cyclic diphosphinite by a formal [4+4] cycloaddition reaction of β-phosphaenone

Unstable β-phosphaenones formed by reaction of the phosphanylidene-σ⁴-phosphorane DmpP = PMe₃ (Dmp = 2,6-dimesitylphenyl) with acenaphthenequinone dimerize in hexane by a formal [4+4] cycloaddition reaction to form a cyclic diphosphinite. X-ray crystallographic analysis and variable temperature ¹H NMR spectra of the cyclic diphosphinite are presented.     

Formation of an η-allyl and a cyclic γ-hydroxyalkyl complex of molybdenum from reaction of MoH2(η-cyclopentadienyl)2 with homoallyl alcohol

The reaction of Cp₂MoH₂ (Cp=η⁵-C₅H₅) with homoallyl alcohol in the presence of a protonic acid afforded a cationic η³-crotyl molybdenum complex and a cyclic α-methyl-γ-hydroxypropyl molybdenum complex. This reaction proceeds via the stepwise formation of the cyclic complex, followed by formation of the η³-crotyl complex.     

Controlled synthesis and functionalization of PEGylated methacrylates bearing cyclic carbonate pendant groups

Homopolymer bearing cyclic carbonate (CC) group, ABA type triblock copolymers, and (AC)B(AC) type terpolymers with statistical arrangement of A and C monomers bearing side chain CC groups are reported here. Difunctional poly(ethylene glycol) macroinitiators (PEGMIs) were prepared from PEG of three different molecular weights. PEGMIs were subsequently used for the preparation of polymers bearing CC pendant groups from cyclic carbonate methacrylate (CCMA) under atom transfer radical polymerization to yield polymers with low polydispersity index. Homopolymer and ABA type triblock copolymers were obtained by polymerizing CCMA monomer and (AC)B(AC) type statistical terpolymers were obtained when methyl methacrylate was included as a comonomer. No polymer was obtained when styrene was used as comonomer. The cyclic carbonate groups were subjected to ring‐opening reaction with monoamine to yield side chain hydroxyurethane polymers with increased solubility and diamines to yield crosslinked insoluble materials. Changes in wettability characteristics were studied by following the water contact angle of the polymers before and after ring‐opening reaction involving the cyclic carbonate pendant group. The polymers which composed of electrolyte in the form of PEG and coordinating species in the form of pendant cyclic carbonate groups showed conductivity in the range of 2–5 × 10^?6 Scm^?1 at 23 °C after doping with lithium bis(trifluoromethane)sulfonimide as characterized by impedance spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1622–1632, 2010     

Inorganic‐Base‐Mediated Hydroamination of Alkenyl Oximes for the Synthesis of Cyclic Nitrones

A method based on hydroamination mediated by inorganic base was developed for the synthesis of cyclic nitrones from alkenyl oximes. DFT calculations of the reaction pathway suggested that this hydroamination could proceed through an unprecedented nucleophilic amination of the unactivated alkene by the oxime nitrogen atom. The transition state of this reaction is stabilized by an ionic interaction between a metal cation such as K⁺ and the oxime oxygen and negatively charged alkene moiety.     

Novel synthesis of cyclic methylvinylsiloxanes by the reaction of methylvinyl diethoxysilane with phosphorous pentachloride

We report a novel synthesis of the cyclic oligomers [(H₂C?CH)(CH₃)SiO]_n obtained by the reaction between phosphorous pentachloride and methylvinyl diethoxysilane. According to gas chromatography/mass spectrometry data, the reaction product consisted of a mixture of cyclic oligomers in which the most important fractions were composed of cycles with n = 5, 6, or 7. The reaction product was also characterized by Fourier transform infrared and ¹H and ¹³C NMR spectroscopy. Experimental results suggested a new kind of reaction between the phosphorous pentachloride and terminal olefins directly bonded to silicon, which was probably associated with sterical effects favoring C? O? Si bond cleavage of ethoxy groups instead of the conventional addition of phosphorous pentachloride to olefinic linkages. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3182–3189, 2002     

An Enzymatic Microdetermination Method for Hydroxylase Cofactor

Abstract

An enzymatic microdetermination method is described to determine the concentration of biologically active hydroxylase cofactor in crude samples. A small amount of hydroxylase cofactor was oxidized and reduced in a cyclic fashion by phenylalanine 4-monooxygenase (EC 1.14.16.1, PheOHase) and dihydropteridine reductase (EC 1.6.99.7, DPRase) in the presence of excess phenylalanine (Phe) and NADH. The amount of NAD⁺, accumulated as a result of this cyclic reaction (first cycling), was in proportion to that of the hydroxylase cofactor. The NAD⁺ was further amplified by an enzymatic amplification reaction, NAD cycling (second cycling) and determined fluorometrically. This double cycling method with more than a 20,000 fold amplification provided extremely high sensitivity, down to 0.02 pmol per assay, and was successfully applied to crude microsamples of pg wet weight.     

Cyclic chronocoulemetry: Disproportionation and dimerization reactions coupled to electron transfer

An extension of double-potential-step chronocoulemetry to multiple or cyclic techniques has been developed, and its potential applications in the study of coupled chemical reactions in electrochemistry are discussed. Disproportionation and dimerization mechnisms are considered. Wroking curves have been calculated with the use of the finite difference digital simulation method. It is shown that better resolution for disproportionation and dimerization reactions can be obtained with cyclic chronocoulometry than with double-potential-step chronocoulemetry. The method has been experimentally verified measuring the disproportionation reaction U(V) in 1 mol dm^?3 sodium hydrogen carbonate solutions. A rate coefficient of 15.6 dm³ mol^?1 was calculated for this reaction.     

Ruthenium(III)‐catalyzed oxidation of cyclopentanol and cyclohexanol by N‐bromoacetamide

Kinetic investigations on Ru(III)‐catalyzed oxidation of cyclopentanol and cyclohexanol by acidic solution of N‐bromoacetamide (NBA) in the presence of mercury(II) acetate as a scavenger have been carried out in the temperature range of 30–45°C. Similar kinetics was followed by both the cyclic alcohols. First‐order kinetics in the lower concentration range of NBA was observed to tend to zero order at its higher concentrations. The reaction exhibits a zero‐order rate dependence with respect to each cyclic alcohol, while it is first order in Ru^III. Increase in [H⁺] and [Cl^?] showed positive effect, while successive addition of acetamide exhibited negative effect on the reaction rate. Insignificant effect of sodium perchlorate, D₂O, and mercury(II) acetate on the reaction velocity was observed. Cationic bromine has been proposed as the real oxidizing species. Various thermodynamic parameters have been computed. A suitable mechanism in agreement with the kinetic observations has been proposed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 275–281, 2005     

Sulfinate‐Salt‐Mediated Radical Relay Cyclization of Cyclic Ethers with 2‐Alkynylbenzonitriles toward 3‐Alkylated 1‐Indenones

A new sulfinate salt‐mediated radical relay for the completion of C(sp³)?H bond indenylation of cyclic ethers with readily available 2‐alkynylbenzonitriles by combining silver/tert‐butyl peroxide (TBHP) was established, providing a wide range of 3‐alkylated 1‐indenones with generally good yields. Interestingly, the current reaction system can tolerate an S‐centered radical and a C‐centered radical in one pot, in which the S‐centered radical promotes the formation of the C‐centered radical to induce a radical cascade without disturbing the reaction process. A reaction mechanism is also proposed based on control experiments.     

Novel Biodegradable Aliphatic Polycarbonate Based on Ketal Protected Dihydroxyacetone

Summary: A novel aliphatic polycarbonate based on ketal protected dihydroxyacetone was synthesized by ring‐opening polymerization of cyclic carbonate monomer, 2,2‐ethylenedioxypropane‐1,3‐diol carbonate (EOPDC), in bulk. Effects of polymerization conditions such as catalysts, catalyst concentration, reaction temperature and reaction time on the polymerization were investigated. The polycarbonate obtained was characterized by GPC, FTIR, ¹H NMR, ¹³C NMR and DSC. The study on in vitro degradation of PEOPDC shows that the degradation mainly results from surface erosion.

Synthesis of an aliphatic polycarbonate with a high molecular weight by ring‐opening polymerization of cyclic carbonate monomer EOPDC.     

The synthesis of the zero-valent nickel complexes via di-π-allylnickel

A new route to zero-valent nickel complexes, (cycloocta-1,5-diene)duroquinonenickel, (endo-dicyclopentadiene)duroquinonenickel, dicycloocta-1,5-dienenickel and bis(tetracyclone)nickel, as described. The synthetic procedure involves the reaction between di-π-allylnickel and duroquinone, cyclic dienes, or tetraphenylcyclopentadienone. The replacement of the π-allyl ligand with duroquinone or a cyclic diene is suggested to follow the associative mechanism. The ¹³C NMR and mass spectra of the compounds isolated are reported.     

Pd/Cu Dual-Catalyzed Asymmetric Synthesis of Highly Functional All-Carbon Quaternary Stereocenters from Vinyl Carbonates

The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp³)−C(sp³) bond formation reactions is reported. The key substrate, a vinyl cyclic carbonate, is activated to provide concomitantly both the requisite nucleophile (by formal umpolung) and electrophile reaction partner preceding the asymmetric cross-coupling process. A wide screening of reaction conditions, additives and catalyst precursors afforded a protocol that gave access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er's) of up to 90 : 10.