Copper-Catalyzed Enantioselective Sonogashira Type Coupling of Alkynes with α-Bromoamides

An asymmetric copper-catalyzed Sonogashira type coupling between alkynes and α-bromoamides has been developed. This method represents a facile approach to synthetically useful β, γ-alkynyl amides from two readily available starting materials in a highly enantioselective manner. A Bisoxazoline diphenylanaline (BOPA) serves as the effective chiral ligand. Preliminary mechanistic studies support the formation of alkyl radical species .     

Terminal Alkyne Coupling Reactions Through a Ring: Effect of Ring Size on Rate and Regioselectivity

Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C₂H₄)][BAr^F₄] (n=12, 14, 16; Ar^F=3,5-(CF₃)₂C₆H₃)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu₂C₆H₃) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH₂)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C₂H₄)][BAr^F₄] and solvent effects.     

Ionic Liquid Iodinating Reagent for Mild and Efficient Iodination of Aromatic and Heteroaromatic Amines and Terminal Alkynes

Hexamethylene bis(N-methylimidazolium) bis(dichloroiodate) (HMBMIBDCI), an ionic liquid iodinating reagent, have been prepared and characterized. Its ability to perform iodination reactions with a variety of substrates has been explored. In general, iodination reactions of aromatic and heteroaromatic amines proceed with good yields in the absence of solvent. Reactions of terminal alkynes in the presence of 1,8-diazabicyclo [5.4.O] undec-7-ene and tetrahydrofuran have been investigated as well.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

插入式永磁低速同步电机非奇异终端滑模观测器设计

提出一种以d-q同步旋转坐标系下, 电流为观测对象的插入式永磁同步电机的非奇异高阶终端滑模观测器, 用来获得高性能矢量控制系统所必需的电机转子位置及速度信息. 采用非奇异终端滑模控制, 提高了观测器的动态响应速度及鲁棒性, 利用高阶滑模控制技术的特性, 有效地抑制了传统滑模控制的抖振现象. 同时给出了转速环及电流环调节器的参数设计方法, 转速环调节器采用积分反馈算法, 电流环调节器使用前馈解耦内模控制技术 ,参数在线调整简单. 将该算法应用到2 MW永磁同步低速电机无传感器控制系统中, 实验结果表明, 该方法能够准确计算出电机的位置和速度, 使系统具有良好的稳态精度和动态性能.     

基于i.MX35的工程机械显示终端设计

工程机械显示终端是重要的人机交互界面,随着工程机械控制系统信息化和智能化水平的不断提高,对车载显示终端也提出了越来越高的要求。为了满足需求,研制了基于i.MX35的工程机械显示终端,该显示终端以i.MX35多媒体应用处理器为核心,采用CODESYS作为应用编程平台,实现了人机界面显示、CAN总线通信、摄像头视频采集、大容量数据存储等功能,具有显示性能强大、启动速度快、应用编程灵活、易于扩展等特点,可以广泛应用于各种工程机械控制系统中。     

端炔与对亚甲基苯醌的1,6-加成

为了合成selaginellin家族天然产物,我们开发了炔锂和对亚甲基苯醌的1,6-加成反应。研究了此反应的反应条件及底物适用范围和限制。结果表明,对亚甲基苯醌苯环上的取代基对反应速率和产率有显著的影响:吸电子基团增加其亲电性,使反应变快,并且可以得到较高的产率;与此相反,给电子基团则降低了对亚甲基苯醌的亲电性,反应变慢,并且表现出可逆性,产率变低。端炔对反应影响很小,均能得到高产率的产物。本方法可用于快速构建selaginellin家族天然产物的骨架结构。     

黑胸大蠊浓核病毒基因组末端序列测定与分析

利用构建的黑胸大蠊浓核病毒(PfDNV)全基因组重组质粒(PfDNV-pUC119)以及一系列完整缺失克隆,通过全自动测序方法完成了PfDNV两末端各728 bp 和730 bp 核苷酸序列的测定. 通过计算机软件分析发现,PfDNV 末端201nt为倒置重复序列,其中最末端122nt为回文序列,能形成典型的发夹结构. 并与同科其它病毒末端序列进行了核苷酸序列同源性比较.     

Application of the Spherical Harmonic Model to the ν(CO) Vibrational Spectra of Some Fe(CO)4 and M(CO)5 (M=Cr, W) Transition Metal Cluster Carbonyl Species

When the Fe(CO)₄ and M(CO)₅ (M=Cr, W) groups are co-ordinated in C_3v and C_4v fashion, respectively, in transition metal carbonyl cluster species they contain two sets of non-symmetry related carbonyl groups. In the application of the spherical harmonic model (SHM) to the interpretation of the infrared spectra of these compounds it proves necessary first to treat these as for a normal, isolated, M(CO)₄ or M(CO)₅ group and then apply the SHM. This recognition gives insights into the general application of the SHM.     

Construction of graphs with given circular flow numbers

Suppose r ≥ 2 is a real number. A proper r‐flow of a directed multi‐graph is a mapping such that (i) for every edge , ; (ii) for every vertex , . The circular flow number of a graph G is the least r for which an orientation of G admits a proper r‐flow. The well‐known 5‐flow conjecture is equivalent to the statement that every bridgeless graph has circular flow number at most 5. In this paper, we prove that for any rational number r between 2 and 5, there exists a graph G with circular flow number r. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 304–318, 2003