Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides

The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes Me_nSiCl_4−n (n=1–3) generates a disilane residue (Me_nSi₂Cl_6−n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes Me_xSiH_yCl_z (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.     

Protonated Porphyrins: Bifunctional Catalysts for the Metal-Free Synthesis of N-Alkyl-Oxazolidinones

The protonation of commercially available porphyrin ligands yields a class of bifunctional catalysts able to promote the synthesis of N-alkyl oxazolidinones by CO₂ cycloaddition to corresponding aziridines. The catalytic system does not require the presence of any Lewis base or additive, and shows interesting features both in terms of cost effectiveness and eco-compatibility. The metal-free methodology is active even with a low catalytic loading of 1 % mol, and the chemical stability of the protonated porphyrin allowed it to be recycled three times without any decrease in performance. In addition, a DFT study was performed in order to suggest how a simple protonated porphyrin can mediate CO₂ cycloaddition to aziridines to yield oxazolidinones.     

Metal‐Free Polymerization of Phenylsilane: Tris(pentafluorophenyl)borane‐Catalyzed Synthesis of Branched Polysilanes at Elevated Temperatures

The strong organoborane Lewis acid B(C₆F₅)₃ catalyzes the polymerization of phenylsilane at elevated temperatures forming benzene and SiH₄ as side‐products. The resulting polymer is a branched polysilane with an irregular substitution pattern, as revealed by 2D NMR spectroscopy. Having explored the mechanism of this novel metal‐free polymerization by computational chemistry methods at the DFT level, we have suggested that unusual cationic active species, namely monomer‐stabilized silyl cations, propagate the polymerization. Hydride abstraction of SiH₃ moiety by the catalyst in the initiation step was found to be kinetically preferred by around 9 kcal mol^?1 over activation by coordination of the monomer at the aromatic ring. The formation of linear Si? Si bonds during propagation was calculated to be less favorable than branching and ligand scrambling, which accounts for the branched and highly substituted form of the polymer that was obtained. This novel type of polymerization bears the potential for further optimization with respect to degree of polymerization and structure control for both primary as well as secondary silanes, which can be polymerized by sterically less hindered boranes.     

One‐Step Synthesis of a [20]Silafullerane with an Endohedral Chloride Ion

Silicon analogues of the most prominent carbon nanostructures, namely, hollow spheroidals such as C₆₀ and the fullerene family, have been unknown to date. Herein we show that discrete Si₂₀ dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through a chloride‐induced disproportionation reaction of hexachlorodisilane in the presence of tri(n‐butyl)amine. X‐ray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement, a thermodynamically preferred substitution pattern according to quantum‐chemical assessment. Our results demonstrate that the wet‐chemical self‐assembly of a complex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si₂ building blocks.     

Significant Substituent Effect on the Anomerization of Pyranosides: Mechanism of Anomerization and Synthesis of a 1,2‐cis Glucosamine Oligomer from the 1,2‐trans Anomer

Aminoglycosides containing a 2,3‐trans carbamate group easily undergo anomerization from the 1,2‐trans glycoside to the 1,2‐cis isomer under mild acidic conditions. The N‐substituent of the carbamate has a significant effect on the anomerization reaction; in particular, an N‐acetyl group facilitated rapid and complete α‐anomerization. The differences in reactivity due to the various N‐substituents were supported by the results of DFT calculations; the orientation of the acetyl carbonyl group close to the anomeric position was found to contribute significantly to the directing of the anomerization reaction. By exploiting this reaction, oligoaminoglycosides with multiple 1,2‐cis glycosidic bonds were generated from 1,2‐trans glycosides in a one‐step process.     

Synthesis,Bonding and Reactivity of a Terminal Titanium Alkylidene Hydrazido Compound

We report a detailed study of the reactions of the Ti?NNCPh₂ alkylidene hydrazide functional group in [Cp*Ti{MeC(NiPr)₂}(NNCPh₂)] ( 8 ) with a variety of unsaturated and saturated substrates. Compound 8 was prepared from [Cp*Ti{MeC(NiPr)₂}(NtBu)] and Ph₂CNNH₂. DFT calculations were used to determine the nature of the bonding for the Ti?NNCPh₂ moiety in 8 and in the previously reported [Cp₂Ti(NNCPh₂)(PMe₃)]. Reaction of 8 with CO₂ gave dimeric [(Cp*Ti{MeC(NiPr)₂}{μ‐OC(NNCPh₂)O})₂] and the “double‐insertion” dicarboxylate species [Cp*Ti‐{MeC(NiPr)₂}{OC(O)N(NCPh₂)C(O)O}] through an initial [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)₂}{N(NCPh₂)C(O)O}], the congener of which could be isolated in the corresponding reaction with CS₂. The reaction with isocyanates or isothiocyanates tBuNCO or ArNCE (Ar=Tol or 2,6‐C₆H₃iPr₂; E=O, S) gave either complete NNCPh₂ transfer, [2+2] cycloaddition to Ti?N_α or single‐ or double‐substrate insertion into the Ti?N_α bond. The treatment of 8 with isonitriles RNC (R=tBu or Xyl) formed σ‐adducts [Cp*Ti{MeC(NiPr)₂}(NNCPh₂)(CNR)]. With Ar^F5CCH (Ar^F5=C₆F₅) the [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)₂}{N(NCPh₂)C(Ar^F5)C(H)}] was formed, whereas with benzonitriles ArCN (Ar=Ph or Ar^F5) two equivalents of substrate were coupled in a head‐to‐tail manner across the Ti?N_α bond to form [Cp*Ti{MeC(NiPr)₂}{N(NCPh₂)C(Ar)NC(Ar)N}]. Treatment of 8 with RSiH₃ (R=aryl or Bu) or Ph₂SiH₂ gave [Cp*Ti{MeC(NiPr)₂}{N(SiHRR′)N(CHPh₂)}] (R′=H or Ph) through net 1,3‐addition of Si? H to the N? N?CPh₂ linkage of 8 , whereas reaction with PhSiH₂X (X=Cl, Br) led to the Ti?N_α 1,2‐addition products [Cp*Ti{MeC(NiPr)₂}(X){N(NCPh₂)SiH₂Ph}].     

Bifunctional (Cyclopentadienone)Iron–Tricarbonyl Complexes: Synthesis,Computational Studies and Application in Reductive Amination

Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knölker’s complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knölker’s complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron–dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium‐labelling experiments and DFT calculations were undertaken and are also presented.     

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis,Characterization and Reactivity of the First Phosphinine Selenide

The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of ¹J_P,Se=883 Hz is in line with a P−Se bond of high s-character. The σ-electron donating Me₃Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C₅H₅P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as ⁱPrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.     

双官能团硫脲催化丙交酯开环聚合反应的理论研究

用密度泛函理论在B3LYP/6-31G(d)水平上研究了双官能团硫脲催化丙交酯开环聚合反应的微观机理. 讨论了催化聚合反应的两条可能路径: 路径A和路径B. 计算结果表明沿路径A进行的开环聚合反应在能量上是有利的. 从理论上证实了催化剂在聚合反应中所起的双官能团催化作用, 即氨基活化引发剂, 硫脲活化单体, 通过两个基团共同作用, 完成催化开环.     

Controlled direct synthesis of C-mono- and C-disubstituted derivatives of [3,3'-Co(1,2-C2B9H11)2]- with organosilane groups: theoretical calculations compared with experimental results

Mono- and dilithium salts of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-), (1(-)), react with different chlorosilanes (Me(2)SiHCl, Me(2)SiCl(2), Me(3)SiCl and MeSiHCl(2)) with an accurate control of the temperature to give a set of novel C(c)-mono- (C(c) = C(cluster)) and C(c)-disubstituted cobaltabis(dicarbollide) derivatives with silyl functions: [1-SiMe(2)H-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (3(-)); [1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (4(-)); [1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (5(-)); [1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (6(-)) and [1,1'-(SiMe(3))(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (7(-)). In a similar way, the [8,8'-mu-(1',2'-C(6)H(4))-1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(9))(2)](-) (8(-)); [8,8'-mu-(1',2'-C(6)H(4))-1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(9))(2)](-) (9(-)) and [8,8'-mu-(1',2'-C(6)H(4))-1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(9))(1',2'-C(2)B(9)H(10))](-) (10(-)) ions have been prepared from [8,8'-mu-(1',2'-C(6)H(4))-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (2(-)). Thus, depending on the chlorosilane, the temperature and the stoichiometry of nBuLi used, it has been possible to control the number of substituents on the C(c) atoms and the nature of the attached silyl function. All compounds were characterised by NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry; [NMe(4)]-3, [NMe(4)]-4 and [NMe(4)]-7 were successfully isolated in crystalline forms suitable for X-ray diffraction analyses. The 4(-) and 8(-) ions, which contain one bridging -mu-SiMe(2) group between each of the dicarbollide clusters, were unexpectedly obtained from the reaction of the monolithium salts of 1(-) and 2(-), respectively, with Me(2)SiHCl at -78 degrees C in 1,2-dimethoxyethane. This suggests that an intramolecular reaction has taken place, in which the acidic C(c)-H proton reacts with the hydridic Si-H, with subsequent loss of H(2). Some aspects of this reaction have been studied by using DFT calculations and have been compared with experimental results. In addition, DFT theoretical studies at the B3 LYP/6-311G(d,p) level of theory were applied to optimise the geometries of ions 1(-)-10(-) and calculate their relative energies. Results indicate that the racemic mixtures, rac form, are more stable than the meso isomers. A good concordance between theoretical studies and experimental results has been achieved.     

The Cyclohexasilanes Si6H11X and Si6Me11X with X=F,Cl, Br and I: A Quantum Chemical and Raman Spectroscopic Investigation of a Multiple Conformer Problem

The conformers of the monohalocyclohexasilanes, Si₆H₁₁X (X=F, Cl, Br or I) and the haloundecamethylcyclohexasilanes, Si₆Me₁₁X (X=F, Cl, Br or I) are investigated by DFT calculations employing the B3LYP density functional and 6‐31+G* basis sets for elements up to the third row, and SDD basis sets for heavier elements. Five minima are found for Si₆H₁₁X—the axial and equatorial chair conformers, with the substituent X either in an axial or equatorial position—and another three twisted structures. The equatorial chair conformer is the global minimum for the X=Cl, Br and I, the axial chair for X=F. The barrier for the ring inversion is ～13 kJ mol^?1 for all four compounds. Five minima closely related to those of Si₆H₁₁X are found for Si₆Me₁₁X. Again, the equatorial chair is the global minimum for X=Cl, Br and I, and the axial chair for X=F. Additionally, two symmetrical boat conformers are found as local minima on the potential energy surfaces for X=F, Cl and Br, but not for X=I. The barrier for the ring inversion is ～14–16 kJ mol^?1 for all compounds. The conformational equilibria for Si₆Me₁₁X in toluene solution are investigated using temperature dependent Raman spectroscopy. The wavenumber range of the stretching vibrations of the heavy atoms X and Si from 270–370 cm^?1 is analyzed. Using the van′t Hoff relationship, the enthalpy differences between axial and equatorial chair conformers (H_ax?H_eq.) are 1.1 kJ mol^?1 for X=F, and 1.8 to 2.8 kJ mol^?1 for X=Cl, Br and I. Due to rapid interconversion, only a single Raman band originating from the “averaged” twist and boat conformers could be observed. Generally, reasonable agreement between the calculated relative energies and the experimentally determined values is found.     

Metal–Ligand Cooperation in Catalytic Intramolecular Hydroamination: A Computational Study of Iridium–Pyrazolato Cooperative Activation of Aminoalkenes

The present study comprehensively explores diverse mechanistic pathways for intramolecular hydroamination of prototype 2,2‐dimethyl‐4‐penten‐1‐amine by Cp*Ir chloropyrazole ( 1 ; Cp*=pentamethylcyclopentadienyl) in the presence of KOtBu base with the aid of density functional theory (DFT) calculations. The most accessible mechanistic pathway for catalytic turnover commences from Cp*Ir pyrazolato (Pz) substrate adduct 2 ?S, representing the catalytically competent compound and proceeds via initial electrophilic activation of the olefin C?C bond by the metal centre. It entails 1) facile and reversible anti nucleophilic amine attack on the iridium–olefin linkage; 2) Ir? C bond protonolysis via stepwise transfer of the ammonium N? H proton at the zwitterionic [Cp*IrPz–alkyl] intermediate onto the metal that is linked to turnover‐limiting, reductive, cycloamine elimination commencing from a high‐energy, metastable [Cp*IrPz–hydrido–alkyl] species; and 3) subsequent facile cycloamine liberation to regenerate the active catalyst species. The amine–iridium bound 2 a ?S likely corresponds to the catalyst resting state and the catalytic reaction is expected to proceed with a significant primary kinetic isotope. This study unveils the vital role of a supportive hydrogen‐bonded network involving suitably aligned β‐basic pyrazolato and cycloamido moieties together with an external amine molecule in facilitating metal protonation and reductive elimination. Cooperative hydrogen bonding thus appears pivotal for effective catalysis. The mechanistic scenario is consonant with catalyst performance data and furthermore accounts for the variation in performance for [Cp*IrPz] compounds featuring a β‐ or γ‐basic pyrazolato unit. As far as the route that involves amine N? H bond activation is concerned, a thus far undocumented pathway for concerted amidoalkene → cycloamine conversion through olefin protonation by the pyrazole N? H concurrent with N? C ring closure is disclosed as a favourable scenario. Although not practicable in the present system, this pathway describes a novel mechanistic variant in late transition metal–ligand bifunctional hydroamination catalysis that can perhaps be viable for tailored catalyst designs. The insights revealed herein concerning the operative mechanism and the structure–reactivity relationships will likely govern the rational design of late transition metal–ligand bifunctional catalysts and facilitate further conceptual advances in the area.     

小肽的合成及其作为双功能螯合剂在诊断用放射性药物中的应用

采用液相合成方法,以很高的纯度和较高的收率合成了3个新的4肽化合物MAG3-Phe-OH,MAG3-Leu-OH和MAG3-Tyr-OH。它们在温和的条件下很容易用99mTc进行标记,并在体内外显示了很高的稳定性。标记物的兔子显象显示新的标记物与99mTc MAG3有不同的代谢途径,有可能对癌细胞有较好的亲合作用而用于肿瘤显像。     

An Organocatalytic Asymmetric Tandem Reaction for the Construction of Bicyclic Skeletons

Cyclic ketones react with (E)‐2‐nitroallylic acetates in the presence of catalytic pyrrolidine‐thiourea, which affords bicyclic skeletons with four or five stereocenters in one single reaction with up to 98 % ee in moderate to high yields. The cooperative effects of both enamine and the Brønsted acid are found to be crucial for the high reactivity and enantioselectivity of this cascade reaction, which is demonstrated by both theoretical calculation and experimental data.