C-H bond functionalization in complex organic synthesis

Direct and selective replacement of carbon-hydrogen bonds with new bonds (such as C-C, C-O, and C-N) represents an important and long-standing goal in chemistry. These transformations have broad potential in synthesis because C-H bonds are ubiquitous in organic substances. At the same time, achieving selectivity among many different C-H bonds remains a challenge. Here, we focus on the functionalization of C-H bonds in complex organic substrates catalyzed by transition metal catalysts. We outline the key concepts and approaches aimed at achieving selectivity in complex settings and discuss the impact these reactions have on synthetic planning and strategy in organic synthesis.     

Activation of alkanes with organotransition metal complexes

Alkanes, although plentiful enough to be considered for use as feedstocks in large-scale chemical processes, are so unreactive that relatively few chemical reagents have been developed to convert them to molecules having useful functional groups. However, a recently synthesized iridium (lr) complex successfully converts alkanes into hydridoalkylmetal complexes (M + R-H --> R-M-H). This is a dihydride having the formula Cp(*)(L)lrH(2), where Cp(*) and L are abbreviations for the ligands (CH(3))(5)C(5) and (CH(3))(3)P, respectively. Irradiation with ultraviolet light causes the dihydride to lose H(2), generating the reactive intermediate Cp(*)lrL. This intermediate reacts rapidly with C-H bonds in every molecule so far tested (including alkanes) and leads to hydridoalkyliridium complexes Cp(*)(L)lr(R)(H). Evidence has been obtained that this C-H insertion, or oxidative addition, reaction proceeds through a simple three-center transition state and does not involve organic free radicals as intermediates. Thus the intermediate Cp(*)lrL reacts most rapidly with C-H bonds having relatively high bond energies, such as those at primary carbon centers, in small organic rings, and in aromatic rings. This contrasts directly with the type of hydrogen-abstraction selectivity that is characteristic of organic radicals. The hydridoalkyliridium products of the insertion reactions can be converted into functionalized organic molecules-alkyl halides-by treatment with mercuric chloride followed by halogens. Expulsion (reductive elimination) of the hydrocarbon from the hydridoalkyliridium complexes can be induced by Lewis acids or heat, regenerating the reactive intermediate Cp(*)lrL. Oxidative addition of the corresponding rhodium complexes Cp(*)RhL to alkane C-H bonds has also been observed, although the products formed in this case are much less stable and undergo reductive elimination at -20 degrees C. These and other recent observations provide an incentive for reexamining the factors that have been assumed to control the rate of reaction of transition metal complexes with C-H bonds-notably the need for electron-rich metals and the proximity of reacting centers.     

Dynamics of conformational transitions in polymers

Conformational transitions in polymers involve large angle rotations about bonds. The process must proceed in a way that does not require gross movements of the macromolecules. The dynamics have been investigated by computer simulation and kinetic theory. The rate-determining step in the transition is found to occur in a mode which is kept local by distortion of nearby parts of the molecule. One especially important type of cooperativity, crank-like counterrotation of second-neighbor bonds, is identified. Experiments which provide evidence about the dynamics of conformational transitions are discussed.     

离子注入水稻干种子光声谱分析

<正> 中国科学院等离子体物理所与安徽省农科院水稻研究所合作,利用高技术——离子注入——于水稻种子诱变育种生物效应的研究,在物理学与生命科学的交叉上做出了有益的尝试。两年多的研究表明:离子注入水稻种子诱变,较其他方法诱变有突变率高、突变谱广的特点。作者认为:荷能粒子注入到水稻干种子中去,不仅有能量交换过程,引起生物体内很强的生理生化反应,而且发生了质量沉积过程,沉积的粒子同生物体分子基团直接键合,改变了生物体原来的分子基团结构。这一切,都会引起水稻种子遗传基因的突变。     

Organic-inorganic hybrid zeolites containing organic frameworks

Organic-inorganic hybrid zeolite materials containing an organic framework have been synthesized by partially superseding a lattice oxygen atom by a methylene group. The use of methylene-bridged organosilane as a silicon source gives zeolite materials containing an organic group as lattice (ZOL), with several zeolitic phases such as the MFI and the LTA structures. Through various characterization methods, the presence of methylene frameworks (Si-CH2-Si) that replace siloxane bonds (Si-O-Si) has been verified, although the Si-C bonds are partly cleaved to give rise to terminal methyl groups. The shape-selective lipophilicity of a ZOL material indicates that it is not a physical mixture of conventional zeolite and amorphous organic-containing material but contains a genuine organic-inorganic hybrid zeolite.     

Iron-stabilized carbocations as intermediates for organic synthesis

Attachment of a transition metal moiety to an olefinic ligand presents the organic chemist with unequaled opportunities to control the regio- and stereospecificities of bond formation. Applications of cationic dienyliron-carbonyl complexes to a range of natural product syntheses have been developed. These applications show how the iron-carbonyl unit directs the regio- and stereochemistry of nucleophile addition. They also show that the iron-carbonyl unit can be used to stabilize otherwise inaccessible carbocations, thereby making them readily available as synthetic intermediates.     

有机农业及有机葡萄病虫害防治

有机农业和有机食品生产在世界上迅速发展,但大众对有机食品的概念、实质内容等的认识上还有许多分歧。在查阅有关资料的基础上,对有机食品的形成过程、有机食品的概念、有机食品在国内外的发展等进行了简单介绍,并对有机食品与绿色食品、无公害食品等进行了比较,同时对有机食品的理解进行了剖析,介绍了我国有机农业中葡萄病虫害的防控经验与实践。     

Actinide organometallic chemistry

The stoichiometric and catalytic chemistry of metal-organic compounds having actinide-to-carbon bonds is in a stage of rapid growth. Chemical, structural, and bonding characteristics have been identified which differ in interesting and informative ways from those of d-block transition element compounds.     

外加碳氮对不同有机碳土壤N2O和CO2排放的影响

以两种有机碳含量不同的土壤为对象,采用室内培养试验方法,研究了外加可溶性碳氮对黄棕壤(高有机碳含量)和紫色土(低有机碳含量)N₂O、CO₂排放的影响。试验设置五种处理分别为:对照(CK),低氮(LN),高氮(HN),低氮配施碳(LNC)和高氮配施碳(HNC).结果表明,土壤有机碳含量较高的黄棕壤各处理N₂O与CO₂排放均高于紫色土。与对照相比,单施氮肥显着促进了两种土壤N₂O排放,紫色土HN处理N₂O排放最高,而黄棕壤LN处理最高;与单施氮肥相比,LNC和HNC处理均显着降低了紫色土N₂O排放,而黄棕壤仅LNC处理N₂O排放显着降低。外源碳的输入显着提高了两种土壤CO₂排放,但单施氮肥对CO₂排放影响不明显。黄棕壤N₂O排放通量与CO₂排放通量呈极显着正相关,而紫色土N₂O排放通量与CO₂排放通量没有相关关系。上述结果说明,外加可溶性碳氮源对土壤呼吸及硝化-反硝化强度有一定的激发效应。     

New strong cement materials: chemically bonded ceramics

New cements developed in recent years have strengths that are greater by an order of magnitude than those of conventional hydraulic cements. These low-temperature materials, whose strengths approach those of many traditional high-temperature ceramics, are termed chemically bonded ceramics. The different routes to generating strong cementitious materials, including warm pressing, chemical modification, high-shear mixing with polymer additions, and the making of fiber and particulate composites, are reviewed. Strength, toughness, durability, impermeability, and abrasion resistance of these new materials have been greatly improved, as have certain electrical and acoustical properties.     

秸秆、木质素及其生物炭对潮土CO2释放及有机碳含量的影响

研究添加秸秆、木质素及其生物炭后潮土CO2释放特征及土壤有机碳含量变化,为合理利用有机物料提供科学依据。采用室内模拟试验,等碳量(1%秸秆/土壤质量比)施入4种物料(秸秆、木质素及其裂解的两种生物炭),分析不同处理土壤CO2释放速率、累积释放量和有机碳、水溶性有机碳(DOC)、易氧化有机碳(ROC)及微生物量碳(MBC)含量的变化与相关性。结果发现,土壤中添加不同物料对土壤CO2释放和有机碳含量有显著影响,秸秆和木质素能提高土壤CO2释放速率、累积释放量及有机碳矿化强度,均达到极显著差异,但两种生物炭处理与对照相比没有显著差异。在培养前期(30 d),不同物料均显著提高了土壤有机碳含量;但培养一年后,仅两种生物炭处理土壤有机碳含量较高,秸秆及木质素与对照相比没有显著差异。秸秆和木质素能显著增加DOC、ROC和MBC等土壤活性有机碳含量,而两种生物炭与对照相比没有明显差异;土壤DOC、ROC(167 mmol·L-1KMn O4)、ROC(33mmol·L-1KMn O4)和MBC直接影响CO2累积释放量,ROC(333 mmol·L-1KMn O4)对CO2累积释放量具有较强的间接作用。相对于秸秆和木质素而言,生物炭增加土壤有机碳含量,而没有增加CO2释放量,因此生物炭农用在固碳减排方面更具有积极意义。     

生物竹炭改良崇明滩涂盐渍化土壤的试验研究

采用小白菜温室盆栽试验方法,研究了生物竹炭对盐渍化土壤的修复和对小白菜生长及其品质的影响。试验共设4个处理:对照、有机肥、生物竹炭、有机肥+生物竹炭。结果表明:生物竹炭有效降低了土壤的电导率,有机肥显著提高了土壤的电导率,生物竹炭与有机肥配施对土壤电导率无影响;生物竹炭使土壤中的总碳、有机质提高,促进了有效磷、速效钾的释放,降低了土壤总可溶性氮的含量,尤其使铵态氮、硝态氮含量显著降低,但土壤酸碱性和含水率无明显变化;生物竹炭处理显著提高了小白菜的株高、生物量和可溶性糖含量,降低了可食用部分的硝酸盐含量。盆栽试验结果显示,生物竹炭具有改良盐渍化土壤、促进小白菜产量增加和品质提高的作用。     

以色列生物有机农业的规划与管理

自上个世纪80年代起,以色列便实现了生物有机农业产品的商业化运作.本文重点介绍了以色列生物有机农业体系内的土壤耕作与培肥措施,以色列的成功经验,对于改造我国的传统农业,建立具有中国特色的有机农业模式,有一定的借鉴意义.     

Supramolecular Archimedean cages assembled with 72 hydrogen bonds

Self-assembly of multiple components into well-defined and predictable structures remains one of the foremost challenges in chemistry. Here, we report on the rational design of a supramolecular cage assembled from 20 ions of three distinct species through 72 hydrogen bonds. The cage is constructed from two kinds of hexagonal molecular tiles, a tris(guanidinium)nitrate cluster and a hexa(4-sulfonatophenyl)benzene, joined at their edges through complementary and metrically matched N-H···O-S hydrogen bonds to form a truncated octahedron, one of the Archimedean polyhedra. The truncated octahedron, with an interior volume of 2200 cubic angstroms, serves as the composite building unit of a body-centered cubic zeolite-like framework, which exhibits an ability to encapsulate a wide range of differently charged species, including organic molecules, transition metal complexes, and "ship-in-a-bottle" nanoclusters not observed otherwise.     

凹凸棒添加对有机肥发酵温度及养分的影响

为充分利用凹凸棒石的吸附性能,降低有机肥发酵过程中的碳氮损失,减少臭气排放,设置4个不同凹凸棒石添加量（0、5%、10%、15%）,探讨凹凸棒石添加量对有机肥发酵温度、养分含量及养分损失率的影响。结果显示：相比不添加凹凸棒石的对照,添加凹凸棒石可降低堆肥发酵最高温度,延长高温持续时间,降低堆体水分损失速率; 5%凹凸棒石添加可显著降低氮素损失约10个百分点,但当其添加量超过10%时,氮素损失反而增加;添加凹凸棒石显著降低了有机质含量和损失率,且凹凸棒石添加量与有机质损失率呈显著负相关关系。此外,添加凹凸棒石可提高有机肥的钾素含量,但对磷素的含量和损失无显著影响。研究表明,有机肥生产工艺中,凹凸棒石的适宜添加量应为物料总质量的5%~10%。     

Mobile point defects and atomic basis for structural transformations of a crystal surface

Structural transformations on elemental semiconductor surfaces typically occur above several hundred degrees Celsius, and the atomic motions involved are extremely rapid and difficult to observe. However, on the (111) surface of germanium, a few lead atoms catalyze atomic motions so that they can be observed with a tunneling microscope at temperatures below 80 degrees C. Mass transport and structural changes are caused by the creation and propagation of both vacancy-like and interstitial-like point defects within the crystal surface. The availability of dangling bonds on the surface is critical. A detailed atomic model for the observed motions has been developed and is used to explain the structural phase transition Ge(111)-c(2x8) <--> 1x1, which occurs near 300 degrees C.     

Free-radical carbon-carbon bond formation in organic synthesis

Organic chemists have begun to use intra- and intermolecular free-radical addition reactions to develop useful synthetic transformations. Carboncentered radicals can form bonds with electron-rich or electron-deficient alkenes, allenes, and acetylenes. Radical addition reactions can also be used to construct hindered carbon-carbon bonds. These characteristics, as well as the large number of functional groups that tolerate free-radical conditions contribute to the importance of such reactions in organic synthesis.     

The motives,benefits, and problems of conversion to organic production

Using data from a survey of certified organic or in-transition to organic vegetable and dairy producers in Canada, we seek to understand a farmer’s decision to convert to organic production by exploring the motives, problems and challenges, and benefits of transition to organic. Results suggest that health and safety concerns and environmental issues are the predominant motives for conversion, while economic motives are of lesser importance. In contrast to the extant literature, results suggest that the motives underlying transition have not changed overtime in Canada. Problems experienced during transition relate to lack of governmental and institutional support, negative pressure from other farmers and farm groups, and lack of physical and financial capital. Reduced exposure to chemicals and improved food quality were highly ranked benefits, while economic related benefits were scored among the lowest of the listed benefits. To prosper, the Canadian organic sector must overcome fundamental marketing problems and challenges. Promulgation of the Canada Organic standard may help address some marketing issues by providing more information to consumers.     

A High-Pressure Test of Birch's Law

The compressional wave velocities of polycrystalline NaCl and KCl have been measured to over 17 gigapascals, with the use of Brillouin scattering and the diamond anvil cell. This pressure corresponds to 40% compression for NaCl and 60% compression for KCl (including the volume change across the B1-B2 transition). The data obey Birch's Law, which predicts that the velocity of each material is linear with density, except across the B1-B2 phase transition in KCl. This deviation from Birch's Law can be rationalized in terms of an interatomic potential model wherein the vibrational frequencies of the nearest neighbor bonds decrease when going to the eight-coordinated B2 structure from the six-coordinated B1 structure.     

基质中有机肥含量对西瓜幼苗生长发育的影响

以草炭、蛭石、珍珠岩一般配方为对照,在基质中添加不同比例有机肥研究其对西瓜育苗的影响。结果表明：15％～20％有机肥处理的西瓜幼苗生长质量较好,壮苗指数及根系活力也较高。