Ruthenium-Catalyzed E-Selective Alkyne Semihydrogenation with Alcohols as Hydrogen Donors

Selective direct ruthenium-catalyzed semihydrogenation of diaryl alkynes to the corresponding E-alkenes has been achieved using alcohols as the hydrogen source. The method employs a simple ruthenium catalyst, does not require external ligands, and affords the desired products in > 99% NMR yield in most cases (up to 93% isolated yield). Best results were obtained using benzyl alcohol as the hydrogen donor, although biorenewable alcohols such as furfuryl alcohol could also be applied. In addition, tandem semihydrogenation-alkylation reactions were demonstrated, with potential applications in the synthesis of resveratrol derivatives

Covalent functionalization of carbon nanotube forests grown in situ on a metal-silicon chip

We report on the successful covalent functionalization of carbon nanotube (CNT) forests, in situ grown on a silicon chip with thin metal contact film as the buffer layer between the CNT forests and the substrate. The CNT forests were successfully functionalized with active amine and azide groups, which can be used for further chemical reactions. The morphology of the CNT forests was maintained after the functionalization. We thus provide a promising foundation for a miniaturized biosensor arrays system that can be easily integrated with Complementary Metal-Oxide Semiconductor (CMOS) technology

Tricarbonyliron(0) complexes of bio-derived η4 cyclohexadiene ligands: An approach to analogues of oseltamivir

We have prepared novel [η4] and [η5]+ tricarbonyliron complexes from an unusual enantiopure cyclohexadiene ligand that possesses a quaternary stereocentre; this in turn is prepared through biotransformation of an aromatic ring. The cyclohexadiene ligand initially possessed two hydroxyl groups, both of which could be substituted with other functionality by means of an overall [η4] → [η5]+ → [η4] → [η5]+ → [η4] sequence. From six novel tricarbonyliron complexes which have been prepared, three have been characterised by x-ray crystallography. The reaction sequence we describe is potentially of relevance to the synthesis of analogues of the anti-influenza drug oseltamivir. In addition, the failure of an attempted addition of a bulky nitrogen nucleophile to an [η5]+ complex sheds light on the limits of reactivity for such additions. Thus, two bulky nucleophiles which are each known to add successfully to unencumbered [η5]+ complexes seemingly cannot be added sequentially to adjacent positions on the cyclohexadiene ligand

Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold

The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43−98% yield. The products were examined with UV− vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle

Palladium-catalyzed stereoselective domino arylation-acylation:an entry to chiral tetrahydrofluorenone scaffolds

A palladium-catalyzed domino arylation-cyclization of biocatalytically derived cyclic 1,3-dienes is demonstrated. The reaction introduces a high degree of structural complexity in a single step, giving access to tricyclic tetrahydrofluorenones with full regio- and stereoselectivity. The transformation proceeds through a novel acylation-terminated Heck-type sequence, and quantum chemical calculations indicate that C-H activation is involved in the terminating acylation step

Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes:Chirality Transfer via a Heck-Type Mechanism

Microbial arene oxidation of benzoic acid with Ralstonia eutropha B9 provides a chiral highly functionalized cyclohexadiene, suitable for further structural diversification. Subjecting this scaffold to a Pd-catalyzed Heck reaction effects a regio- and stereoselective arylation of the cyclohexadiene ring, with 1,3-chirality transfer of stereogenic information installed in the microbial arene oxidation. Quantum chemical calculations explain the selectivity both by a kinetic preference for the observed arylation position and by reversible carbopalladation in competing positions. Further product transformation allowed the formation of a tricyclic ketone possessing four stereogenic centers. This demonstrates the capability of the method to introduce stereochemical complexity from planar nonchiral benzoic acid in just a few steps

Chiral 1,5-disubstituted 1,2,3-triazoles-versatile tools for foldamers and peptidomimetic applications

1,4- A nd 1,5-Disubstituted triazole amino acid monomers have gained increasing interest among peptidic foldamers, as they are easily prepared via Cu- A nd Ru-catalyzed click reactions, with the potential for side chain variation. While the latter is key to their applicability, the synthesis and structural properties of the chiral mono-or disubstituted triazole amino acids have only been partially addressed. We here present the synthesis of all eight possible chiral derivatives of a triazole monomer prepared via a ruthenium-catalyzed azide alkyne cycloaddition (RuAAC). To evaluate the conformational properties of the individual building units, a systematic quantum chemical study was performed on all monomers, indicating their capacity to form several low energy conformers. This feature may be used to effect structural diversity when the monomers are inserted into various peptide sequences. We envisage that these results will facilitate new applications for these artificial oligomeric compounds in diverse areas, ranging from pharmaceutics to biotechnology

Release of Terminal Alkynes via Tandem Photodeprotection and Decarboxylation of o -Nitrobenzyl Arylpropiolates in a Flow Microchannel Reactor

Photocleavable protecting groups (PPGs) offer a complementary protection paradigm compared to traditional protection groups. Herein, an o-nitrobenzyl (NB) PPG was employed to protect a variety of arylpropiolic acids. Upon a cascade of light-triggered photodeprotection in a microchannel reactor (residence times of 100-500 s), followed by Cu-catalyzed decarboxylation at 60 \ub0C, the NB-protected arylpropiolic acid afforded a terminal alkyne. This terminal alkyne was further reacted in situ with an azide via click chemistry to yield a 1,2,3-triazole in a one-pot reaction. Furthermore, the effect of different substituents (methyl, vinyl, allyl, and phenyl) at the benzylic position on the rate of photodeprotection was studied. The quantum yields of photolysis for the benzylic-substituted esters were determined to be as high as 0.45 compared to the unsubstituted ester with a 0.08 quantum yield of photolysis

Turn-off mode fluorescent norbornadiene-based photoswitches

Single-molecule fluorescence emission of certain positive photochromic systems such as diarylethenes have been exploited for biological imaging and optical memory storage applications. However, there is a lack of understanding if negative photochromic systems can be used for such type of applications. Hence, to explore the potential of negative photochromic molecules for possible optical memory storage applications, we have here synthesized and studied a series of four norbornadiene-quadricyclane (NBD-QC) photoswitching molecules. These molecules feature either linearly conjugated or cross-conjugated pi-electron systems. Upon photoisomerization, the UV-vis absorption spectra of the molecules revealed a strong blue shift in the QC-form, with a photoisomerization quantum yield close to 80% for the cross-conjugated systems. In contrast, a strong intrinsic emission (up to Φf= 49%) for the linearly conjugated compounds in the NBD form was observed. Upon light-induced isomerization, the emission was completely turned off in the QC-form in all the compounds studied. Further, the robustness of the system was evaluated by performing several switching cycles. Under nitrogen, the emission can be turned off and recovered with almost no loss of emission. We also show that the QC-form can be photochemically triggered to convert back to the NBD-form using a low energy UV light (340 nm), allowing an all optical conversion to both species. The demonstrated properties can make the NBD-QC system attractive for potential applications such as optical memory storage devices

Selective Iron-Mediated C- and O-Addition of Phenolic Nucleophiles to a Cyclohexadiene Scaffold Using Renewable Precursors

Renewable phenols have been investigated as nucleophiles for the addition to a cationic cyclohexadienyl iron carbonyl scaffold. Benign conditions compatible with solvents such as ethanol and water were developed, and for the first time, selective C- or O-addition could be achieved. In addition, a novel atom-economic approach to forming the C-addition products directly from the neutral precursor complex in a single step using a catalytic acid is described. The formed C-addition product could then be selectively demetalated to form one of two different product classes, a functionalized arene or a cyclohexadiene