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.     

Net oxidative addition of C(sp3)-F bonds to iridium via initial C-H bond activation

Carbon-fluorine bonds are the strongest known single bonds to carbon and as a consequence can prove very hard to cleave. Alhough vinyl and aryl C-F bonds can undergo oxidative addition to transition metal complexes, this reaction has appeared inoperable with aliphatic substrates. We report the addition of C(sp(3))-F bonds (including alkyl-F) to an iridium center via the initial, reversible cleavage of a C-H bond. These results suggest a distinct strategy for the development of catalysts and promoters to make and break C-F bonds, which are of strong interest in the context of both pharmaceutical and environmental chemistry.     

Formation of catalytic metal-molecule contacts

We describe a new strategy for the in situ growth of molecular wires predicated on the synthesis of a trifunctional "primed" contact formed from metal-carbon multiple bonds. The ruthenium-carbon pi bond provides structural stability to the molecular linkages under ambient conditions, and density functional calculations indicate the formation of an efficient conduit for charge carriers to pass between the metal and the molecule. Moreover, the metal-carbon pi bond provides a chemically reactive site from which a conjugated molecular wire can be grown in situ through an olefin metathesis reaction.     

Organometallic chemistry in homogeneous catalysis

Many reactions catalyzed by soluble transition metal compounds proceed by way of organometallic intermediates, even though the original catalyst may be a simple salt. This generality is illustrated for three industrial syntheses of acetic acid that use homogeneous catalysts. Some developments in organometallic chemistry that may extend the utility of homogeneous catalysis are photoactivation of catalysts and the recognition of the importance of metallacyclic intermediates.     

Isolable compounds containing a silicon-silicon double bond

After 70 years of unsuccessful attempts, several stable disilene-compounds with double bonds between silicon atoms-have now been made. The silicon-silicon double bond resembles in many ways the well-known carbon-carbon double bond of organic chemistry. However, striking dissimilarities are also found between disilenes and alkenes in both their structures and chemical reactions.     

Supramolecular chemistry: receptors, catalysts, and carriers

Supramolecular chemistry is the study of the structures and functions of the supermolecules that result from binding substrates to molecular receptors. Macropolycyclic receptors and coreceptors have been designed that form cryptate inclusion complexes and display molecular recognition towards spherical, tetrahedral, and linear substrates of various kinds (metal cations, inorganic anions, and organic or biological cations or anions). Anion binding has led to the development of anion coordination chemistry. Metalloreceptors simultaneously bind organic molecules and metal ions; speleands combine polar and nonpolar binding subunits. Receptors bearing reactive functional groups may act as molecular reagents or catalysts, performing a chemical transformation on the bound substrates (by such reactions as hydrogen transfer, ester cleavage, and protoadenosinetriphosphatase and protokinase activities). Receptors fitted with lipophilic groups can operate as molecular carriers, translocating bound species through a membrane; this transport can be coupled to chemical potentials (proton and redox gradients).     

Solar Energy Conversion by Water Photodissociation: Transition metal complexes can provide low-energy cyclic systems for catalytic photodissociation of water

The basic concepts for direct and catalyzed photodissociation of water have been summarized. Water dissociation in closed-cycle processes based on endothermic photochemical reactions offers a potential solution to the solar energy conversion problem. Transition metal complexes, whose excited state chemistry is extremely rich (23, 24) although mostly unexplored, are, in principle, suitable "catalysts" for cycles of this type. The most interesting cycles are those involving metal hydrido complexes or binuclear complexes in which the two metal atoms are bound into a macrocyclic ligand. Systematic investigations of the photochemistry of transition metal complexes with the aim of designing suitable systems for solar energy conversion have long-range promise and merit further consideration.     

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.     

风化煤腐植酸增效尿素红外光谱分析

采用碱性混合活化剂处理风化煤,研制腐植酸添加剂,按不同比例添加到尿素熔融液中,采用模拟喷浆造粒的方法,制备3类增效尿素。通过风化煤与添加剂、尿素与增效尿素红外光谱特征对比发现:风化煤经过活化后,碳单键数量降低,碳链缩短,活性腐植酸HA类提取物出现活性官能团,FR类除单键数量减少和碳链缩短外,生成部分胺、酰胺结构;增效剂与尿素在反应过程中,出现了三键和累积双键破坏、稳定性复合物形成、碳链缩短、双键结构增加等变化,但不同类型增效剂对产品红外光谱特征影响存在差异。     

Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.     

Tetramesityldisilene, a stable compound containing a silicon-silicon double bond

Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air. Like the olefins of carbon chemistry, tetramesityldisilene undergoes addition reactions across the silicon-silicon double bond.     

Enols and other reactive species

Rapid advances in the chemistry of enols and other reactive species have been made possible recently by the development of methods for generating these short-lived substances in solution under conditions where they can be observed directly and their reactions can be monitored accurately. New laboratory techniques are described and a sample of the new chemistry they have made available is provided; special attention is given to ynols and ynamines and the remarkable effects that the carbon-carbon triple bonds of these substances have on their acid-base properties.     

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.     

Asymmetric hydrogenation of unfunctionalized, purely alkyl-substituted olefins

Asymmetric hydrogenation of olefins is one of the most useful reactions for the synthesis of optically active compounds, especially in industry. However, the application range of the catalysts developed so far is limited to alkenes with a coordinating functional group or an aryl substituent next to the double bond. We have found a class of chiral iridium catalysts that give high enantioselectivity in the hydrogenation of unfunctionalized, trialkyl-substituted olefins. Because these catalysts do not require the presence of any particular functional group or aryl substituent in the substrate, they considerably broaden the scope of asymmetric hydrogenation.     

Ambient-temperature isolation of a compound with a boron-boron triple bond

Homoatomic triple bonds between main-group elements have been restricted to alkynes, dinitrogen, and a handful of reactive compounds featuring trans-bent heavier elements of groups 13 and 14. Previous attempts to prepare a compound with a boron-boron triple bond that is stable at ambient temperature have been unsuccessful, despite numerous computational studies predicting their viability. We found that reduction of a bis(N-heterocyclic carbene)-stabilized tetrabromodiborane with either two or four equivalents of sodium naphthalenide, a one-electron reducing agent, yields isolable diborene and diboryne compounds. Crystallographic and spectroscopic characterization confirm that the latter is a halide-free linear system containing a boron-boron triple bond.     

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.     

Molecular transformations on single crystal metal surfaces

One of the primary objectives of modern surface chemistry of transition metals is the synthesis of surface compounds and complexes and the understanding of their reactivity, structure, and bonding. Such considerations are paramount for advancing understanding of catalysis, adhesion, organic thin-film growth, and electrocatalysis. On selected metals, particularly copper, silver, and gold, selective scission of X-H bonds (where X is oxygen, carbon, nitrogen, or sulfur) by surface-bound atomic oxygen occurs to form moderately stable species that can be isolated for further study. Selective oxidation reactions may occur heterogeneously by means of this novel oxygen- activated route. Furthermore, this selective chemistry offers a paradigm for synthesis of a wide variety of surface organometallic complexes, whose formation can be predicted from acid-base principles. These subjects are discussed in this article with emphasis on their role in catalytic oxidation cycles.     

Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex

Cleavage of the relatively inert dinitrogen (N(2)) molecule, with its extremely strong N identical withN triple bond, has represented a major challenge to the development of N(2) chemistry. This report describes the reductive cleavage of N(2) to two nitrido (N(3-)) ligands in its reaction with Mo(NRAr)(3), where R is C(CD(3))(2)CH(3) and Ar is 3,5-C(6)H(3)(CH(3))(2'), a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion (with N identical withN bond cleavage) to the nitrido molybdenum(VI) product N identical withMo(NRAr)(3) followed first-order kinetics at 30 degrees C. It is proposed that the cleavage reaction proceeds by way of an intermediate complex in which N(2) bridges two molybdenum centers.     

Strong interactions in supported-metal catalysts

Many commercially important catalysts consist of small metal particles dispersed on inorganic oxide surfaces. Although in most cases there is no significant interaction between the metal and the support, strong bonding can be demonstrated in a recently discovered class of supported-metal catalysts. These cases typically involve group VIII metals dispersed on transition metal oxides whose surfaces can be reduced to form cations with lower valences. Spectroscopic measurements indicate that an electron is transferred from the cation (such as Ti(3+) or Nb(4+)) to the metal particle. This, in turn, leads to profound changes in the catalytic and chemisorption properties and the morphology of the metal particles.     

H 2O和H 2 S与双卤分子形成的卤键的理论研究

用量子化学从头算方法对H2O和H2S与卤素分子(X—Y)形成的卤键O/S…X—Y进行了理论研究.计算结果表明,卤键的形成导致X—Y键长增大与伸缩振动频率红移;电子密度拓扑(AIM)分析表明,复合物中的卤键为闭壳层相互作用;自然键轨道(NBO)分析表明,卤键O/S…X—Y形成时,强的分子间超共轭n(O/S)→σ*(X—Y)引起的电荷转移是X—Y键伸缩振动频率红移的重要原因.