Silica‐Bound 3‐{2‐[Poly(ethylene Glycol)]ethyl}‐Substituted 1‐Methyl‐1H‐imidazol‐3‐ium Bromide: A Recoverable Phase‐Transfer Catalyst for Smooth and Regioselective Conversion of Oxiranes to β‐Hydroxynitriles in Water

A series of β‐hydroxynitriles were efficiently synthesized from the regioselective ring opening of oxiranes by cyanide anion in the presence of silica‐bound 3‐{2‐[poly(ethylene glycol)]ethyl}‐substituted 1‐methyl‐1H‐imidazol‐3‐ium bromide (SiO₂? PEG? ImBr) as a novel recoverable phase‐transfer catalyst in H₂O (Scheme 1 and Table 2). The workup procedure was straightforward, and the catalyst could be reused over four times with almost no loss of catalytic activity and selectivity.     

A Fused Benzocyclooctene Ring System via an Aromatic Cope Rearrangement: Thermal Reactions of trans‐1‐Aryl‐2‐ethenylcyclobutanecarbonitriles

The results of an aromatic Cope rearrangement of a trans‐1‐aryl‐2‐ethenylcyclobutanecarbonitrile are reported (Scheme). The use of this rearrangement for the construction of the fused benzocyclooctene ring system and a preliminary study of the electronic requirements to favor such a transformation are also described.     

A Ring Expansion Strategy in Antiviral Synthesis: A Novel Approach to TAK‐779

Abstract

A synthesis of TAK‐779 that relies on construction of a key carboxylic acid intermediate by a ring expansion with TMSCHN₂ is described.     

Development of a general approach to the synthesis of a library of isoflavonoid derivatives

Isoflavonoids are a class of organic compounds that act primarily as antioxidants. They are produced almost exclusively by various members of the bean family including soybeans, tofu, peanuts, chick peas, and alfalfa. The antioxidant characteristics that isoflavonoids exhibit help hinder the progression of certain cancers, primarily breast, prostate, and colon cancer. We have developed a three-five step synthesis for obtaining a suite of isoflavonoid derivatives. The synthesis involves an enamine formation, a ring closure and halogenation, a Suzuki coupling, and finally a global deprotection to obtain the respective isoflavonoid derivatives.     

Understanding the acceleration in the ring-opening of lactones delivered by microwave heating

This paper reports the first detailed study focussed upon identifying the influence that microwave heating (MWH) has upon the mechanic steps involved in the tin catalysed ring-opening of lactones such as ?-caprolactone (CL). Direct comparison of conventional (CH) and microwave (MWH) heated kinetic studies showed that a key factor in the reduction of the polymerisation cycle time with MWH was the elimination of the induction period associated with in situ catalyst manufacture and initiation. NMR studies demonstrated that the most significant mechanistic change contributing to the observed induction time reduction/elimination was faster initiation (i.e., reaction of the initiatior/catalyst complex with the first monomer unit). Consequently, analysis of the dielectric properties of the reaction components predicted that this MWH induced change was related to the selective volumetric heating of both the catalyst and the monomer. Furthermore, this indication of the greater significance of the initiation step in defining the length of the induction period suggests that this is the rate determining step of the process, whether conducted by CH or MWH. Increasing the catalyst concentration was demonstrated to produce significant reductions in reaction heat-up time and to induce a significant (up to 30 °C) overshoot in reaction mixture bulk temperature in with MWH only. Thus supporting the conclusion that selective heating of the organometallic species in the system contributes directly to differences in the reaction conditions and which need to be taken into account when drawing comparisons with CH systems. Consequently, both effects were concluded to be thermally generated from selective volumetric heating.     

Ring opening of epoxides with alcohols using Fe(Cp)2BF4 as catalyst

Fe(Cp)₂BF₄ is an efficient catalyst for the alcoholysis of aromatic, aliphatic, and cyclic epoxides giving excellent yields of the corresponding β-alkoxy alcohols under ambient conditions. The methanolysis of styrene oxide using Fe(Cp)₂BF₄ as a catalyst (5 mol %) gave excellent yield of 2-methoxy-2-phenylethanol with complete regio-selectivity. The ring opening of cyclic epoxides gave 77–97% yields of trans-β-methoxy alcohols, in 0.5–6 h. The use of 1,2-epoxyhexane and 1,2-epoxydodecane as substrates gave both regioisomers in excellent yields. The first order rate of reaction with respect to catalyst was observed for the kinetics of ring opening of 1,2-epoxyhexane with methanol.     

Formal and total synthesis of (±)-cycloclavine

A ring fragmentation and intramolecular azomethine ylide 1,3-dipolar cycloaddition sequence of reactions was successfully used in the preparation of a known (±)-cycloclavine precursor in good overall yield. Results of efforts to incorporate the tetrasubstituted cyclopropane ring present in cycloclavine are also discussed.     

A practical and efficient synthesis of 6-carboalkoxy-13-cycloalkyl-5H-indolo[2,1-a][2]benzazepine-10-carboxylic acid derivatives

A convenient and practical synthesis of 6-carboalkoxy-13-cycloalkyl-5H-indolo[2,1-a][2]benzazepine-10-carboxylic acid derivatives (6) has been developed. The key step in the synthesis utilizes an intramolecular tandem reaction sequence of a Michael addition followed by a Horner–Wadsworth–Emmons (HWE) olefination reaction between hemi-aminal 11 and methyl 2-(dimethoxyphosphoryl)acrylate 12. The ring construction occurred efficiently and purification of the products 6 was straightforward. The C-10 methyl ester of 6a was hydrolyzed selectively to the carboxylic acid 13 while the olefin of 6d was converted to the cyclopropane 14 using trimethylsulfoxonium iodide in DMSO in the presence of NaH.     

Successive approximation-like 4-bit full-optical analog-to-digital converter based on Kerr-like nonlinear photonic crystal ring resonators

Implementing of photonic sampling and quantizing analog-to-digital converters (ADCs) enable us to extract a single binary word from optical signals without need for extra electronic assisting parts. This would enormously increase the sampling and quantizing time as well as decreasing the consumed power. To this end, based on the concept of successive approximation method, a 4-bit full-optical ADC that operates using the intensity-dependent Kerr-like nonlinearity in a two dimensional photonic crystal (2DPhC) platform is proposed. The Silicon (Si) nanocrystal is chosen because of the suitable nonlinear material characteristic. An optical limiter is used for the clamping and quantization of each successive levels that represent the ADC bits. In the proposal, an energy efficient optical ADC circuit is implemented by controlling the system parameters such as ring-to-waveguide coupling coefficients, the ring’s nonlinear refractive index, and the ring’s length. The performance of the ADC structure is verified by the simulation using finite difference time domain (FDTD) method.     

激光陀螺磁灵敏度特性研究

分析、计算了激光陀螺的磁灵敏度特性,并进行了磁灵敏度试验.试验结果及分析表明：在腔体加工准确度不变的情况下,采用合理的设计可以大大降低激光陀螺在某些方向上的磁灵敏度,同时磁试验结果对于设计激光陀螺的磁屏蔽结构具有一定的实用价值.