Selective, nickel-catalyzed hydrogenolysis of aryl ethers

Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>Ar-OMe>ArCH(2)-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.     

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.     

C-O bond formation by polyketide synthases

Polyketide synthases (PKSs) assemble the polyketide carbon backbone by sequential decarboxylative condensation of acyl coenzyme A (CoA) precursors, and the C-C bond-forming step in this process is catalyzed by the beta-ketoacyl synthase (KS) domain or subunit. Genetic and biochemical characterization of the nonactin biosynthesis gene cluster from Streptomyces griseus revealed two KSs, NonJ and NonK, that are highly homologous to known KSs but catalyze sequential condensation of the acyl CoA substrates by forming C-O rather than C-C bonds. This chemistry can be used in PKS engineering to increase the scope and diversity of polyketide biosynthesis.     

Designed synthesis of 3D covalent organic frameworks

Three-dimensional covalent organic frameworks (3D COFs) were synthesized by targeting two nets based on triangular and tetrahedral nodes: ctn and bor. The respective 3D COFs were synthesized as crystalline solids by condensation reactions of tetrahedral tetra(4-dihydroxyborylphenyl) methane or tetra(4-dihydroxyborylphenyl)silane and by co-condensation of triangular 2,3,6,7,10,11-hexahydroxytriphenylene. Because these materials are entirely constructed from strong covalent bonds (C-C, C-O, C-B, and B-O), they have high thermal stabilities (400 degrees to 500 degrees C), and they also have high surface areas (3472 and 4210 square meters per gram for COF-102 and COF-103, respectively) and extremely low densities (0.17 grams per cubic centimeter).     

Helix signals in proteins

The alpha helix, first proposed by Pauling and co-workers, is a hallmark of protein structure, and much effort has been directed toward understanding which sequences can form helices. The helix hypothesis, introduced here, provides a tentative answer to this question. The hypothesis states that a necessary condition for helix formation is the presence of residues flanking the helix termini whose side chains can form hydrogen bonds with the initial four-helix greater than N-H groups and final four-helix greater than C-O groups; these eight groups would otherwise lack intrahelical partners. This simple hypothesis implies the existence of a stereochemical code in which certain sequences have the hydrogen-bonding capacity to function as helix boundaries and thereby enable the helix to form autonomously. The three-dimensional structure of a protein is a consequence of the genetic code, but the rules relating sequence to structure are still unknown. The ensuing analysis supports the idea that a stereochemical code for the alpha helix resides in its boundary residues.     

Membranes as the energy source in the endergonic transformation of vitamin A to 11-cis-retinol

The eye needs to biosynthesize 11-cis-retinoids because the chromophore of rhodopsin is 11-cis-retinal. The critical metabolic step is the endergonic isomerization of free all-trans-retinol (vitamin A) into 11-cis-retinol. This isomerization process can take place in isolated membranes from the retinal pigment epithelium in the absence of added energy sources. Specific binding proteins probably do not serve as an energy source, and since all of the reactions in the visual cycle are shown here to be reversible, trapping reactions also do not participate in the isomerization reaction. One previously unexplored possibility is that the chemical energy in the bonds of the membrane itself may drive the isomerization reaction. A group transfer reaction is proposed that forms a retinyl ester from a lipid acyl donor and vitamin A. This transfer can drive the isomerization reaction because the all-trans-retinyl ester is isomerized directly to 11-cis-retinol. Thus, the free energy of hydrolysis of the ester is coupled to the thermodynamically uphill trans to cis isomerization. The prediction of an obligate C-O bond cleavage in the vitamin A moiety during isomerization is borne out. Although the natural substrate for isomerization is not known, all-trans-retinyl palmitate is processed in vitro to 11-cis-retinol by pigment epithelial membranes.     

纳米CuI催化偶联反应合成二苯醚类农药中间体

二苯醚是一种重要的农药中间体,通过W/O微乳法,制备出形貌均一的球状纳米CuI,并应用于催化C-O交叉偶联反应中,在温和的反应条件下,合成了具有优良产率的二苯醚类化合物,该方法可在今后的农药合成中应用。     

A stable bicyclic compound with two Si=Si double bonds

In contrast to carbon, silicon does not readily form double bonds, and compounds containing silicon-silicon double bonds can usually be stabilized only by protection with bulky substituents. We have isolated a silicon analog of spiropentadiene 1, a carbon double-ring compound that has not been isolated to date. In the crystal structure of tetrakis[tri(t-butyldimethylsilyl)silyl]spiropentasiladiene 2, a substantial deviation from the perpendicular arrangement of the two rings is observed, and the silicon-silicon double bonds are shown to be distorted. Spectroscopic data indicate pronounced interaction between two remote silicon-silicon double bonds in the molecule. Silicon-silicon bonds may be more accessible to synthesis than previously assumed.     

Lateral hopping of molecules induced by excitation of internal vibration mode

We demonstrate electron-stimulated migration for carbon monoxide (CO) molecules adsorbed on the Pd(110) surface, which is initiated by the excitation of a high-frequency (HF) vibrational mode (C-O stretching mode) with inelastic tunneling electrons from the tip of scanning tunneling microscopy. The hopping phenomenon, however, cannot be detected for CO/Cu(110), even though the hopping barrier is lower than in the CO/Pd(110) case. A theoretical model, which is based on the anharmonic coupling between low-frequency modes (the hindered-translational mode related to the lateral hopping) and the HF mode combined with electron-hole pair excitation, can explain why the hopping of CO is observed on Pd(110) but not on Cu(110).     

Raney Ni-Sn catalyst for H2 production from biomass-derived hydrocarbons

Hydrogen (H2) was produced by aqueous-phase reforming of biomass-derived oxygenated hydrocarbons at temperatures near 500 kelvin over a tin-promoted Raney-nickel catalyst. The performance of this non-precious metal catalyst compares favorably with that of platinum-based catalysts for production of hydrogen from ethylene glycol, glycerol, and sorbitol. The addition of tin to nickel decreases the rate of methane formation from C-O bond cleavage while maintaining the high rates of C-C bond cleavage required for hydrogen formation.     

Charging effects on bonding and catalyzed oxidation of CO on Au8 clusters on MgO

Gold octamers (Au8) bound to oxygen-vacancy F-center defects on Mg(001) are the smallest clusters to catalyze the low-temperature oxidation of CO to CO2, whereas clusters deposited on close-to-perfect magnesia surfaces remain chemically inert. Charging of the supported clusters plays a key role in promoting their chemical activity. Infrared measurements of the stretch vibration of CO adsorbed on mass-selected gold octamers soft-landed on MgO(001) with coadsorbed O2 show a red shift on an F-center-rich surface with respect to the perfect surface. The experiments agree with quantum ab initio calculations that predict that a red shift of the C-O vibration should arise via electron back-donation to the CO antibonding orbital.     

腐植酸对水体中五价钒的吸附

采用批次实验法,研究了腐植酸浓度、钒离子浓度、吸附时间、温度、溶液p H、离子强度、电解质等对腐植酸吸附水体中五价钒的影响。结果表明,钒溶液浓度为90.91 mg·L~(-1)条件下,腐植酸的浓度为1.09 g·L~(-1)时,腐植酸对钒的吸附量最大。随着钒溶液浓度的增加,吸附率逐渐降低并趋于0;而吸附量呈增加-缓慢增加-平衡的趋势;在腐植酸浓度为1.09 g·L~(-1)条件下,钒溶液浓度为1 818.18 mg·L~(-1)时,吸附量达到最大值,吸附等温线与Langmuir模型基本吻合。随着溶液pH、温度的增加,腐植酸对钒的吸附量逐渐减少,即在酸性、温度较低的条件下更有利于腐植酸对钒的吸附。随着溶液电解质浓度的增加,腐植酸对钒的吸附量逐渐降低。红外光谱和扫描电镜的结果显示,腐植酸对钒的吸附机制为钒在腐植酸的表面和内部形成稳定的络合物,这与腐植酸的O-H(或N-H)的氢键、C-O和C-H键的伸缩振动有关。因此,可以考虑用适量的腐植酸作吸附剂,去除水体中的钒,并调整环境条件增强吸附效果。     

Tyrosinase reactivity in a model complex: an alternative hydroxylation mechanism

The binuclear copper enzyme tyrosinase activates O2 to form a mu-eta2:eta2-peroxodicopper(II) complex, which oxidizes phenols to catechols. Here, a synthetic mu-eta2:eta2-peroxodicopper(II) complex, with an absorption spectrum similar to that of the enzymatic active oxidant, is reported to rapidly hydroxylate phenolates at -80 degrees C. Upon phenolate addition at extreme temperature in solution (-120 degrees C), a reactive intermediate consistent with a bis-mu-oxodicopper(III)-phenolate complex, with the O-O bond fully cleaved, is observed experimentally. The subsequent hydroxylation step has the hallmarks of an electrophilic aromatic substitution mechanism, similar to tyrosinase. Overall, the evidence for sequential O-O bond cleavage and C-O bond formation in this synthetic complex suggests an alternative intimate mechanism to the concerted or late stage O-O bond scission generally accepted for the phenol hydroxylation reaction performed by tyrosinase.     

Dynamics-driven reaction pathway in an intramolecular rearrangement

A critical role is traditionally assigned to transition states (TSs) and minimum energy pathways, or intrinsic reaction coordinates (IRCs), in interpreting organic reactivity. Such an interpretation, however, ignores vibrational and kinetic energy effects of finite temperature. Recently it has been shown that reactions do not necessarily follow the intermediates along the IRC. We report here molecular dynamics (MD) simulations that show that dynamics effects may alter chemical reactions even more. In the heterolysis rearrangement of protonated pinacolyl alcohol Me3C-CHMe-OH2+ (Me, methyl), the MD pathway involves a stepwise route with C-O bond cleavage followed by methyl group migration, whereas the IRC pathway suggests a concerted mechanism. Dynamics effects may lead to new interpretations of organic reactivity.     

Highly regioselective amination of unactivated alkanes by hypervalent sulfonylimino-λ³-bromane

Amination of alkanes has generally required metal catalysts and/or high temperatures. Here we report that simple exposure of a broad range of alkanes to N-triflylimino-λ(3)-bromane 1 at ambient temperature results in C-H insertion of the nitrogen functionality to afford triflyl-substituted amines in moderate to high yields. Marked selectivity for tertiary over secondary C-H bonds was observed; primary (methyl) C-H bonds were inert. Addition of hexafluoroisopropanol to inhibit decomposition of 1 dramatically improved the C-H amination efficiencies. Second-order kinetics, activation parameters (negative activation entropy), deuterium isotope effects, and theoretical calculations suggest a concerted asynchronous bimolecular transition state for the metal-free C-H amination event.     

花生蛋白高水分挤压组织化过程中的化学键变化

 【目的】从挤压产品微观结构、化学键变化和蛋白质酰化改性等方面，探讨花生蛋白高水分挤压组织化结构的形成机理。【方法】采用扫描电子显微镜观察挤压产品的微观结构，利用物性测定仪分析挤压产品的质构特性，用化学分析方法对蛋白质中的总巯基和二硫键含量进行分析，采用琥珀酰化的方法对花生蛋白进行酰化处理。【结果】蛋白质溶解度试验结果显示，随挤压温度的升高，花生蛋白的溶解度迅速降低，在含2%SDS和2%SDS+2%2-ME缓冲液中的溶解度显著增加，最高达76.89%（140℃），说明挤压产品中以非共价键结合的蛋白质含量显著增加。随挤压温度的增加，二硫键含量在140～150℃范围内呈缓慢下降趋势，在155℃时显著降低。花生蛋白质酰化后，挤压产品的硬度、咀嚼度和组织化度等显著降低，相应的微观结构也显示出显著的变化。【结论】在花生蛋白高水分挤压组织化过程中，疏水作用和氢键起主要作用，其次是二硫键。在挤压过程中，花生蛋白分子内原有的二硫键含量降低，可能发生了部分断裂，高温会加速该反应的进行。酰化改性明显干扰了蛋白质分子间的相互作用，不利于挤压产品良好组织化结构的形成。     

Sex attractant of the codling moth: characterization with electroantennogram technique

trans-8, trans-10-Dodecadien-1-ol is a sex attractant of the codling moth, Laspeyresia pomonella. Antennal responses (electroantennograms) to a series of monounsaturated compounds were used in determining the location and configuration of the two double bonds. The synthetic compound is very attractive to male codling moths in the field.     

Internal rotation and spin conversion of CH3OH in solid para-hydrogen

The quantum solid para-hydrogen (p-H2) has recently proven useful in matrix isolation spectroscopy. Spectral lines of compounds embedded in this host are unusually narrow, and several species have been reported to rotate in p-H2. We found that a p-H2 matrix inhibits rotation of isolated methanol (CH3OH) but still allows internal rotation about the C-O bond, with splittings of the E/A torsional doublet in internal rotation-coupled vibrational modes that are qualitatively consistent with those for CH3OH in the gaseous phase. This simplified high-resolution spectrum further revealed the slow conversion of nuclear spin symmetry from species E to species A in the host matrix, offering potential insight into nuclear spin conversion in astrophysical sources.     

屈服条件下木材微观结构的变化

试验研究了红松木材在纵向压应力屈服条件下微观结构的变化。结果表明：与素材相比，屈服条件下试样的自由基浓度显著增加，碳含量相对减少，氧含量相对增加；由压应力产生的机械自由基主要来源于纤维素主键Ｃ－Ｏ键的断裂。     

Hydrodefluorination of perfluoroalkyl groups using silylium-carborane catalysts

Carbon-fluorine bonds are among the most unreactive functionalities in chemistry. Interest in their activation arises in part from the high global warming potentials of anthropogenic polyfluoroorganic compounds. Conversion to carbon-hydrogen bonds (hydrodefluorination) is the simplest modification of carbon-fluorine bonds, but efficient catalytic hydrodefluorination of perfluoroalkyl groups has been an unmet challenge. We report a class of carborane-supported, highly electrophilic silylium compounds that act as long-lived catalysts for hydrodefluorination of trifluoromethyl and nonafluorobutyl groups by widely accessible silanes under mild conditions. The reactions are completely selective for aliphatic carbon-fluorine bonds in preference to aromatic carbon-fluorine bonds.