环氧烷化合物在有机合成中的应用

综述了近年来环氧烷化合物在有机合成中的应用。环氧烷化合物的开环反应可以用来合成其它方法难以合成的多官能团化合物，或通过开环和修饰合成其他环状化合物。另外，利用该反应还可以提供保护基以及立体、区域选择性地合成各种有机化合物。参考文献23篇。     

Enzymatic degradation of highly phenolic lignin-based polymers (lignophenols)

Enzymatic degradation of two lignin-based polymers (lignophenols), lignocatechol and lignocresol, prepared by selectively grafting catechol and p-cresol to C_α positions of lignin, respectively, were carried out in aqueous organic solvents. Both lignophenols showed high reactivity in the peroxidase-catalyzed oxidation. Structural analyses by NMR spectroscopies revealed that the degraded lignophenols contained aliphatic chain content, which might be mainly formed in the reduction of the intermediate initially generated by the aromatic ring cleavage. Lower amount of aromatic units in the lignophenols after degraded by peroxidase also indicted the cleavage of aromatic rings. Due to the substitution of phenols at C_α positions of lignin, the degraded lignophenols did not have carbonyl structure, which was abundant in the biodegradation products of native lignin. The two lignophenols were also degraded by Rhus vernicifera laccase. But the degree of degradation was lower than that of the degradation by peroxidase, which might be due to the low activity of laccase on the lignin moieties in lignophenols.     

Base- and light-assisted synthesis of anthracenes from 3-allylnaphthalene-2-carbaldehydes

The synthesis of substituted anthracenes from naphthalene precursors is described. The key step involved heating ortho-allyl substituted naphthalene-2-carbaldehydes and potassium t-butoxide in DMF with concomitant irradiation from a high pressure mercury lamp to afford anthracenes in yields of 76-98%.     

Selective methodologies for the synthesis of biologically active piperidinic compounds

The synthesis of optically active substituted piperidines has been achieved by using four different methodologies. The first one is an intramolecular nucleophilic displacement of activated alcohol moieties that was used to build up the piperidine ring of (-)-prosophylline and (-)-slaframine, and the second one is a ring-closing metathesis of unsaturated amines which was employed in the synthesis of (+)-sedamine and 4a,5-dihydrostreptazoline. The third methodology is the alpha-functionalization of N-Boc piperidines which was particularly useful in the synthesis of argatroban, and the fourth one is a ring expansion of prolinols to 3-chloropiperidines or 3-hydroxypiperidines which was utilized to synthesize (-)-paroxetine, (-)-pseudoconhydrine, the piperidine ring of (-)-velbanamine and (+)-zamifenacin.     

分次环的分次Jacobson根

本文通过引入弱拟正则元的概念，对一般Ｍｏｎｏｉｄ分次环Ａ（未必有１）给出以内部元素刻划的分次Ｊａｃｏｂｓｏｎ根ＪＧ（Ａ）．证明当Ａ有１时，ＪＧ（Ａ）与通常定义的Ｊｇ（Ａ）相等．对ＪＧ（Ａ）性质的讨论，推广了最近的许多结果．作为应用，我们给出了Ａｒｔｉｎ分次环的全部基本结构定理．     

Synthesis of Azabicyclic Building Blocks for Daphniphyllum Alkaloid Intermediates Featuring N‐Trichloroacetyl Enamide 5‐endo‐trig Radical Cyclizations

A general procedure is reported for the synthesis of cis ring fused azapolycyclic compounds bearing an all‐carbon quaternary stereocenter at the ring fusion and an adequate functionalization for the assembly of new rings leading to advanced synthetic intermediates for Daphniphyllum alkaloid synthesis. The key carbon?carbon bond‐forming step in this approach is a radical cyclization of an N‐cycloalkenyl trichloroacetamide derivative involving a tetrasubstituted enamide to achieve polyfunctionalized lactams.     

Nanoscale C‐Rich SixC1−x Bus/Ring Waveguide Based Cross‐Wavelength Data Converter

The carbon‐rich silicon carbide (C‐rich Si_xC_1?x) micro‐ring channel waveguide with asymmetric core aspect is demonstrated for all‐optical cross‐wavelength pulsed return‐to‐zero on‐off keying (PRZ‐OOK) data conversion. Enhanced nonlinear optical Kerr switching enables 12‐Gbit per second data processing with optimized modulation depth. The inverse tapered waveguide at end‐face further enlarges the edge‐coupling efficiency, and the asymmetric channel waveguide distinguishes the polarization modes. To prevent data shape distortion, the bus/ring gap spacing is adjusted to control the quality factor (Q‐factor) of the micro‐ring. Designing the waveguide cross section at 500 × 350 nm² provides the C‐rich Si_xC_1?x channel waveguide to induce strong transverse electric mode (TE‐mode) confinement with a large Kerr nonlinearity of 2.44 × 10^?12 cm² W^?1. Owing to the trade‐off between the Q‐factor and the on/off extinction ratio, the optimized bus/ring gap spacing of 1400 nm is selected to provide a coupling ratio at 5–6% for compromising the modulation depth and the switching throughput. Such a C‐rich Si_xC_1?x micro‐ring with asymmetric channel waveguide greatly enhances the cross‐wavelength data conversion efficiency to favor its on‐chip all‐optical data processing applications for future optoelectronic interconnect circuits.     

A High‐Efficiency All‐Fiber Laser Operated in High‐Order Mode using Ring‐Core Yb‐Doped Fiber

An all‐fiber laser generating a cylindrical vector beam is proposed and demonstrated using a home‐made ring‐core Yb‐doped fiber (RC‐YDF). In the RC‐YDF, not only annular doping but also ring‐type beam pump is realized. This is believed to be the first report describing the realization of annular doping and ring‐type beam pump in active fiber simultaneously, which can enhance the efficiency for high‐order mode oscillation. This laser operates in the high‐order mode stably with a slope efficiency of as high as 55.7%. Cylindrical vector modes can be obtained easily through adjusting the polarization controller. This work may have great potential for providing high‐efficiency and high‐power cylindrical vector beam and vortex beam sources.     

摩擦磨损试验机模拟活塞环-缸套摩擦行为的功能开发

参考活塞环-缸套的实际运行条件,结合SRV-4摩擦磨损试验机自身的性能特点和工作原理,通过开发设计,增加合理的硬件及软件测试条件,实现摩擦磨损试验机模拟活塞环-缸套摩擦行为的功能.系统测试结果表明：功能开发后的摩擦磨损试验机可在较短时间内获得活塞环-缸套摩擦副性能优劣的试验数据,满足快速、直观评价活塞环-缸套的摩擦磨损性能的需要,在活塞环-缸套摩擦副研究中具有重要的应用价值.     

Designing of energetic miktoarm A2B2 star‐shaped polymer by means of click chemistry and ROP techniques

Novel A₂B₂‐type energetic miktoarm star‐shaped copolymers composed of two PGN arms and two PCL arms was synthesized by the combination of ring‐opening polymerization (ROP) and “click” chemistry. Initially, diazido end‐functionalized two‐arm PGN, (PGN)₂‐(N₃)₂, was synthesized by ROP of glycidyl nitrate monomers. Subsequently, (PGN)₂‐(PCL)₂ was obtained from the click reaction between diazido end‐functionalized (PGN)₂‐(N₃)₂ polymers and propargyl‐terminated poly(ε‐caprolactone) (PTPCL). This star copolymer solves problems of PCL (lake of energy) and PGN (low T_g). The Fourier‐transform infrared (FT‐IR), ¹H nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) studies revealed that (PGN)₂‐(PCL)₂ was successfully obtained. The thermal behavior of star polymer was investigated by thermogravimetric analysis (TGA) and derivative thermogravimetry. The results show that (PGN)₂‐(PCL)₂ decomposed at two stages. The first stage is seen at 212.6°C which related to degradation of –ONO₂ group and second stage attributed to degradation of PCL group which is seen at 346.1°C.