Controlling the Scholl reaction

Guidelines for the application of the Scholl reaction were developed. Labeling experiments demonstrate that the Scholl reaction fails in small, unsubstituted oligophenylenes (e.g., o-terphenyl) due to oligomerization of the products (e.g., triphenylene). Incorporation of suitably placed blocking groups (e.g., t-butyl) suppresses oligomerization. The well-established directing group effects in electrophilic aromatic substitution predict the outcome of Scholl reactions of substituted substrates. Activating o,p-directing groups (e.g., MeO) direct bond formation o,p, either intramolecularly or intermolecularly. Deactivating o,p-directing groups (e.g., Br) also direct bond formation o,p but yields are lower. Deactivating m-directors (e.g., NO2) suppress reaction. MoCl5 and PhI(OOCCF3)2/BF3.Et2O are general and effective reagents for the Scholl oxidation. Calculations (B3LYP/6-31G(d)) predict the Scholl reaction in alkoxyarenes to proceed via arenium cations, not radical cations. Suzuki-Miyaura couplings were used to generate 12 substituted o-terphenyl derivatives.     

Synthesis of fused tetrazole derivatives via a tandem cycloaddition and N-allylation reaction and parallel synthesis of fused tetrazole amines

A method for the synthesis of novel fused tricyclic tetrazoles from allylic bromides generated by the recently discovered DiazAll reaction has been developed. This new tandem reaction comprises a cycloaddition between a nitrile and (TMS)N(3) followed by an intramolecular N-allylation. The variation of functionalities in the benzene moiety was well-tolerated, and only a moderate difference in yield and degree of purity was noticed. An exo-methylene group in these new compounds permitted further derivatization. Structural resemblance with substances which possess important pharmacological properties motivated the synthesis of a series of ketones and a small library of amines.     

Carborane functionalized pyrroles and porphyrins via the Suzuki cross-coupling reaction

A new route to carboranylated pyrroles and porphyrins is reported which involves the Suzuki coupling of readily available bromo- and boronic acid-pyrroles and bromoporphyrins with functionalized carboranes; the X-ray structures of two targeted products are presented and discussed.     

Enantioselective synthesis of fused dihydropyranones via squaramide-catalyzed Michael addition/lactonization cascade reaction

A highly enantioselective (49–99% ee) Michael addition/lactonization cascade process has been developed to construct 3,4-dihydropyran-2-one in the presence of a bifunctional squaramide. Various α,β-unsaturated N-acyl heterocycles were well tolerated and afforded 3,4-dihydropyran-2-ones in moderate to excellent isolated yields (50–99%). Both cyclic and acyclic β-diketones functioned as appropriate donors. The resulting 3,4-dihydropyran-2-ones could be readily converted into oxadecalinones.     

Nanocrystal-micelle: synthesis, self-assembly and application

Nanocrystals (NCs) are one of the important building blocks for fabrication of nanostructured arrays for wide range of optical, electronic, magnetic, catalytic and biosensing applications. Here, our recent advances in the synthesis, self-assembly and application of NC-micelles are highlighted. The NCs are encapsulated inside the core of surfactant micelles in a rapid, interfacially driven micro-emulsion process. The flexible surface chemistry of the NC-micelles causes them to be water-soluble and allows further self-assembly into two- and three-dimensional ordered arrays. The NC-micelles are biocompatible, of interest for bio-labeling. Finally, integration of the ordered arrays and charge transport property are discussed.     

Organic synthesis in the solid state via hydrogen-bond-driven self-assembly

This Perspective describes how chemists can control intermolecular [2 + 2] photodimerizations in the solid state using small molecules as linear templates. The templates assemble olefins into positions for the reaction via hydrogen-bond-driven self-assembly. We attach functional groups to the olefins that complement hydrogen bond donor and acceptor groups of the templates. The resulting cyclobutane-based products form stereospecifically, quantitatively, and in gram amounts. The templates are used to direct the formation of a [2.2]paracyclophane and ladderanes. The organic solid state is an exciting medium within which to control chemical reactivity since it is possible to synthesize, or construct, molecules that may be, otherwise, unobtainable from solution. The products form with a high degree of stereocontrol provided by a crystal lattice. The critical covalent-bond-forming process also occurs in a solvent-free environment. That molecules are virtually frozen in position in a solid also means that this methodology enables chemists to employ principles of molecular recognition and self-assembly to direct and conduct organic synthesis.     

The self-assembly and lyotropic mesomorphism of riboguanylic acids (GMP)

The three isomeric guanylic acids (5'-GMP, 3'-GMP and 2'-GMP) and the 3':5'-cyclic derivative (cGMP) form, in water solution, left-handed columnar aggregates which, at higher concentration, pack to give left-handed cholesteric mesophases. The self-assembly process and liquid crystal formation are discussed in relation to the behaviour of the 2'-deoxy analogues.     

In-situ synthesis of nanoparticles via supersolubilizing micelle self-assembly

In-situ synthesis of nano-particles using the self-assembly of molten salt and super soluble micellae was proposed based on a phenomenon of super solubilization of molten salt in reverse micellae and its self-assembly when the concentration reached up to 95%(w/w).The mechanism of the self-assembly indicates that the self-assembly of molten salt occurs in a reverse micelle where a homogenous phase is established between 5%(w/w)of a surfactant with a VB value of less than 1 and a hydrocarbon spe- cies.This synthesis has some unique features,such as being free of water,highly effective deposition and narrow distribution of particle size.     

Design, synthesis, and crystallographic studies of neutral platinum-based macrocycles formed via self-assembly

A series of neutral, platinum-based macrocycles was synthesized from rigid oxygen donor building blocks via self-assembly. The combination of a platinum-based 60 degrees acceptor unit 1 with several linear and angular dicarboxylate bridging ligands afforded hitherto unknown neutral platinum-based supramolecular triangles and rhomboids. In addition, a similar reaction of the diplatinum molecular clip 6 and three different linear dicarboxylates led to the formation of neutral molecular rectangles. Most of the macrocycles were characterized by X-ray single-crystal structure analysis, and, in all cases, NMR spectra were consistent with the formation of single highly symmetrical species.     

Novel synthesis of fused isoxazolidines via a palladium catalysed allene insertion-intramoleculer 1,3-dipolar cycloaddition cascade reaction

A one pot, three component palladium catalysed allenation of aryl iodides, in combination with a nitrone cycloaddition, leads to formation of fused isoxazolidines, creating two rings, two stereocentres and one tetrasubstituted carbon centre.     

Triazole-linked dendro[60]fullerenes: modular synthesis via a ‘click’ reaction and acidity-dependent self-assembly on the surface

A series of Fréchet-type dendron functionalized [60]fullerene derivatives that bear a 1,2,3-triazole linkage group, referred to as triazole-linked dendro[60]fullerenes, were prepared via a modular synthetic protocol based on a Cu-catalyzed [3+2] cycloaddition (‘click’) reaction. Electronic properties of these dendro[60]fullerenes were investigated by UV-vis spectroscopy and cyclic voltammetry. Interfacial supramolecular self-assembly behavior of these dendro[60]fullerenes was studied using atomic force microscopy (AFM). The resulting self-assemblies showed different nanoscale packing geometries and morphologies on the surface, which are controllable by parameters such as the generation of dendron, the nature of peripheral functionalities, and the experimental conditions (e.g., acidity) applied. Correlations between molecular structure and self-assembling outcome were surveyed and discussed. The results of this study suggest a new avenue to gain better ‘bottom-up’ control over the self-assembly of dendrimer-fullerene hybrid materials in terms of shape and size.     

Photophysical properties of unsymmetric meso-substituted porphyrins synthesized via the Suzuki coupling reaction

A new family of porphyrins containing different groups in meso positions was synthesized by Suzuki coupling reaction of meso mono- and dibromo-diarylporphyrins with several boronate esters, catalyzed by palladium organometallic complexes. These procedures gave high yields of unsymmetric porphyrins bearing carboxylate anchoring groups, with enhanced absorptions in the red and showing no tendency for aggregation in toluene or THF solutions. Such properties are of interest for application in dye-sensitized solar cells.     

Fully fused boron-doped polycyclic aromatic hydrocarbons: their synthesis,structure–property relationships,and self-assembly behavior in aqueous media

Planarized triarylboranes are attracting increasing attention not only as models of boron-doped graphenes, but also as promising materials for organic optoelectronics. In particular, polycyclic aromatic hydrocarbon (PAH) skeletons with embedded boron atom(s) in the inner positions are of importance in light of their high chemical stability and π-stacking ability derived from their planar geometries. Herein, we disclose a robust synthesis of such fully fused boron-doped PAHs and their self-assembly behavior in aqueous media to explore their potential utility in biological applications. The synthesis using in situ-generated planar diarylboranes as a key precursor afforded a series of fully fused boron-doped PAHs, even including an amphiphilic derivative with hydrophilic side chains. These compounds exhibited red emission in solution, and slight structural modification resulted in increased fluorescence brightness. While these compounds showed relatively low Lewis acidity compared to their partially ring-fused counterparts, their Lewis acidities were slightly increased in polar solvents compared to those in nonpolar solvents. In addition, their B–N Lewis acid–base adducts, even those with a strong, charge-neutral Lewis base such as N,N-dimethylaminopyridine (DMAP), exhibited photo-dissociation behavior in the excited state. The amphiphilic derivative showed significant spectral changes with increased water content in DMSO/H₂O mixed media and formed sheet-like aggregates. The disassembly and assembly processes of the aggregates were externally controlled by the addition of DMAP and an acid, accompanied by a change in the fluorescence intensity.

A series of fully fused boron-doped polycyclic aromatic hydrocarbons is synthesized. Self-assembly of an amphiphilic derivative can be controlled by addition of a Lewis base or an acid in aqueous media.     

Divergent synthesis of fused Benzo-xanthene and oxazine derivatives via Cu-catalyst

Cu-Cu₂O combination showed synergic effects in catalyzing intramolecular Ullmann coupling reaction for halo-Betti bases to afford fused benzo-xanthenes from both electron-rich and electron-deficient aromatic systems in good yield under mild reaction conditions. The sterically hindered halo-Betti bases also provided products in excellent yield. Under optimized condition, a gram scale reaction was also performed to afford the product in excellent yield. However, without ortho-halo substituted Betti-bases failed to afford fused benzo-xanthene derivatives. Exploring the reaction optimization without Cu metal, serendipitously it was produced 1,3-oxazine derivatives in excellent yield via intramolecular cross-dehydrogenative coupling (CDC) reaction. Similarly, electron-rich, electron-deficient and sterically hindered Betti-bases provided the products in good to excellent yield under mild condition.     

Rational synthesis, self-assembly, and optical properties of PbS-Au heterogeneous nanostructures via preferential deposition

High-quality, monodisperse PbS-Au(1), PbS-Au(4), and PbS-Au(n) nanostructures have been synthesized via a facile and convenient solution chemistry approach. HRTEM images of these nanostructures showed good selectivity of gold deposition on the semiconductor in several spatially correlated directions. The formation of these regular nanostructures can be explained by the difference in polarity of crystal facets that led to the selective growth of metal on the semiconductor surface. Owing to their narrow size distribution and intrinsic high-symmetry, the resulting PbS-Au(4) and PbS-Au(n) heterogeneous nanostructures could spontaneously self-assemble into ordered arrays with different symmetries. From the results of the pump-probe measurements, the presence of Au in PbS-Au(4) nanostructures has substantially altered the nonlinear optical response of PbS nanocrystals.     

1,4-palladium migration via C-H activation, followed by arylation: synthesis of fused polycycles

A novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.     

Large-scale synthesis of alkyne-linked tripodal porphyrins via palladium-mediated coupling conditions

Suzuki and Sonogashira couplings have been used in short and efficient sequences to give access to a new family of porphyrin trimers on a practical scale.