Oxyreactive thermal analysis

The paper presents the applicability of Oxyreactive Thermal Analysis (OTA) for the investigation of different kinds of carbon matter. For comparative reasons and more precise interpretation, along with OTA some physico-chemical properties of analyzed materials were used as the methods commonly applied for the investigations. The carbon materials of both natural (anthracites, graphite and diamonds) and synthetic origin (active carbon, glass carbon, expanded graphite, soot and synthetic diamonds) were investigated. It was stated that there is close relationship between structure parameters and physico-chemical properties and the thermal reactivity within the investigated groups of carbon matters. The results show that OTA can be accepted as a good investigative way for such materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dialkyl Ether Formation by Nickel‐Catalyzed Cross‐Coupling of Acetals and Aryl Iodides

A new substrate class for nickel‐catalyzed C(sp³) cross‐coupling reactions is reported. α‐Oxy radicals generated from benzylic acetals, TMSCl, and a mild reductant can participate in chemoselective cross‐coupling with aryl iodides using a 2,6‐bis(N‐pyrazolyl)pyridine (bpp)/Ni catalyst. The mild, base‐free conditions are tolerant of a variety of functional groups on both partners, thus representing an attractive C? C bond‐forming approach to dialkyl ether synthesis. Characterization of a [(bpp)NiCl] complex relevant to the proposed catalytic cycle is also described.     

Spontaneous Reconstitution of Functional Transmembrane Proteins During Bioorthogonal Phospholipid Membrane Synthesis

Transmembrane proteins are critical for signaling, transport, and metabolism, yet their reconstitution in synthetic membranes is often challenging. Non‐enzymatic and chemoselective methods to generate phospholipid membranes in situ would be powerful tools for the incorporation of membrane proteins. Herein, the spontaneous reconstitution of functional integral membrane proteins during the de novo synthesis of biomimetic phospholipid bilayers is described. The approach takes advantage of bioorthogonal coupling reactions to generate proteoliposomes from micelle‐solubilized proteins. This method was successfully used to reconstitute three different transmembrane proteins into synthetic membranes. This is the first example of the use of non‐enzymatic chemical synthesis of phospholipids to prepare proteoliposomes.     

Chemical Synthesis Elucidates the Immunological Importance of a Pyruvate Modification in the Capsular Polysaccharide of Streptococcus pneumoniae Serotype 4

Carbohydrate modifications are believed to strongly affect the immunogenicity of glycans. Capsular polysaccharides (CPS) from bacterial pathogens are frequently equipped with a pyruvate that can be placed across the 4,6‐, 3,4‐, or 2,3‐positions. A trans‐2,3‐linked pyruvate is present on the CPS of the Gram‐positive bacterium Streptococcus pneumoniae serotype 4 (ST4), a pathogen responsible for pneumococcal infections. To assess the immunological importance of this modification within the CPS repeating unit, the first total synthesis of the glycan was carried out. Glycan microarrays containing a series of synthetic antigens demonstrated how antibodies raised against natural ST4 CPS specifically recognize the pyruvate within the context of the tetrasaccharide repeating unit. The pyruvate modification is a key motif for designing minimal synthetic carbohydrate vaccines for ST4.     

An Indoxyl‐Based Strategy for the Synthesis of Indolines and Indolenines

An indoxyl‐based strategy for the synthesis of indolines and indolenines via unprecedented aza‐pinacol and aza‐semipinacol rearrangements was developed. This method provides direct access to the core structures of several classes of indole alkaloids. The synthetic utility was demonstrated by the divergent synthesis of an array of functionalized polycyclic structures from a common intermediate and the formal total synthesis of the indoline natural product minfiensine. The reversed reactivity of indoxyl as a building block compared to that of indole offers a conceptually distinct disconnection strategy for indoline‐ and indolenine‐containing heterocycles and natural products.     

Surface‐Specific Functionalization of Nanoscale Metal–Organic Frameworks

A method for modifying the external surfaces of a series of nanoscale metal–organic frameworks (MOFs) with 1,2‐dioleoyl‐sn‐glycero‐3‐phosphate (DOPA) is presented. A series of zirconium‐based nanoMOFs of the same topology (UiO‐66, UiO‐67, and BUT‐30) were synthesized, isolated as aggregates, and then conjugated with DOPA to create stably dispersed colloids. BET surface area analysis revealed that these structures maintain their porosity after surface functionalization, providing evidence that DOPA functionalization only occurs on the external surface. Additionally, dye‐labeled ligand loading studies revealed that the density of DOPA on the surface of the nanoscale MOF correlates to the density of metal nodes on the surface of each MOF. Importantly, the surface modification strategy described will allow for the general and divergent synthesis and study of a wide variety of nanoscale MOFs as stable colloidal materials.     

Cobalt‐Catalyzed Cross‐Coupling of 3‐ and 4‐Iodopiperidines with Grignard Reagents

A cobalt‐catalyzed cross‐coupling between 3‐ and 4‐iodopiperidines and Grignard reagents is disclosed. The reaction is an efficient, cheap, chemoselective, and flexible way to functionalize piperidines. This coupling was used as the key step to realize a short synthesis of (±)‐preclamol. Some mechanistic investigations were conducted that highlight the formation of radical intermediates.     

A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions

We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a ¹⁵N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process.     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

Nickel(II) complexes of bidentate N-heterocyclic carbene/phosphine ligands: efficient catalysts for Suzuki coupling of aryl chlorides

Nickel(II) complexes of bidentate N-heterocyclic carbene (NHC)/phosphane ligand L were prepared and structurally characterized. Unlike palladium, which forms [PdCl(2)(L)], the stable nickel product isolated is the ionic [Ni(L)(2)]Cl(2). These Ni(II) complexes are highly robust in air. Among different N-substituents on the ligand framework, the nickel complex of ligand L bearing N-1-naphthylmethyl groups (2 a) is a highly effective catalyst for Suzuki cross-coupling between phenylboronic acid and a range of aryl halides, including unreactive aryl chlorides. The activities of 2 a are largely superior to those of other reported nickel NHC complexes and their palladium counterparts. Unlike the previously reported [NiCl(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane), 2 a can effectively catalyze the cross-coupling reaction without the need for a catalytic amount of PPh(3), and this suggests that the PPh(2) functionality of hybrid NHC ligand L can partially take on the role of free PPh(3). However, for unreactive aryl chlorides at low catalyst loading, the presence of PPh(3) accelerates the reaction.