Divergent Synthesis of Oxa-Cyclic Nitrones through Gold(I)-Catalyzed 1,3-Azaprotio Transfer of Propargylic α-Ketocarboxylate Oximes: Experimental and DFT Studies

1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally.     

Iron mediated cathodic electrosynthesis of hausmannite nanoparticles

A novel synthetic route has been proposed to prepare hausmannite nanoparticles. The synthetic route comprises an iron mediated constant current cathodic electrodeposition of manganite and heat treatment of the latter to obtain hausmannite. The obtained nanostructures have been characterized using X-ray Diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and Fourier transform Infrared Spectrometry (FTIR). The role of iron in the formation of manganite precursor has been studied by cyclic voltammetry (CV) and differential thermal analysis (DTA). A formation mechanism based on iron mediated formation of Mn³⁺ and subsequent cathodic reduction of the disproportionated products has been proposed accordingly. The prepared nanoparticles exhibited specific capacitance of 143 F g⁻¹ in 0.5 M Na₂SO₄ solution. The retained specific capacity was 87% after 2000 cycles.     

Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Unlocking the Drug Potential of the Bryostatin Family: Recent Advances in Product Synthesis and Biomedical Applications

Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014–present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1 , the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development.     

Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Hydrothermal Synthesis and Structure of a Novel Coordination Polymer Co_3(tma)(pda)_2(H_2O)_3]n·nH_2O

1INTRODUCTION Recently,the design and preparation of coordina-tion polymers with new porous frameworks are of great interest due to their potential functionalities such as catalysis,gas absorption,separation and molecu-lar recognition.In designing1-D,2-D and3-D porous coordination polymers,the selection of appropriate ligands is crucial for determining the structure.The mixed-linker systems of both carboxylates and pyri-dyls have proved to be effective for the preparation of novel coordi…     

基站智能天线多波束合成技术

采用数字波束形成的技术，给出了基站智能天线多波束合成的有效算法。对圆环阵分布的基站天线多波束方向图进行了综合，得到了空间隔离度很好的多个波束，并将副瓣控制在30dB以下，结果令人满意。该方法可用于任意单元构成的不均匀阵列天线，还可用于波束展宽及扇形波束的合成。     

基于TC8830AF的智能语音卡结构与设计

本文描述一种基于８０３１单片机和ＴＣ８８３０ＡＦ语音处理器的ＰＣ机智能语音卡，通过软硬件设计解决了ＰＣ－８０３１－ＴＣ８８３０ＡＦ结构中的通讯问题。该语音卡在进行语音的合成、编辑和播放时，仅占用极少的ＰＣ机ＣＰＵ处理时间，能满足计算机系统进行实时语音合成的要求。