A5039577293- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Porphyrin and Phthalocyanine Chemistry
- Synthesis and Properties of Aromatic Compounds
- Luminescence and Fluorescent Materials
- Asymmetric Synthesis and Catalysis
- Coordination Chemistry and Organometallics
- Catalytic Cross-Coupling Reactions
- Oxidative Organic Chemistry Reactions
- Synthetic Organic Chemistry Methods
- Catalytic C–H Functionalization Methods
- Radical Photochemical Reactions
- Chemical Synthesis and Reactions
- Metal-Catalyzed Oxygenation Mechanisms
- Surface Chemistry and Catalysis
- Organoboron and organosilicon chemistry
- Cyclopropane Reaction Mechanisms
- Fullerene Chemistry and Applications
- Crystallography and molecular interactions
- Catalytic Alkyne Reactions
- Vanadium and Halogenation Chemistry
- Fluorine in Organic Chemistry
- Photochromic and Fluorescence Chemistry
- Sulfur-Based Synthesis Techniques
- Organic Electronics and Photovoltaics
Nagoya University
2016-2025
Graduate School USA
2013-2021
Aichi University
2016
Kyoto University
2004-2014
Tohoku University
2006-2014
Yonsei University
2006-2014
Osaka University
2006-2012
Mitsubishi Chemical Group Science and Technology Research Center (Japan)
2012
The University of Tokyo
2012
Japan Science and Technology Agency
2004-2010
Round the twist: Metalation of [36]octaphyrin 1 provided Möbius aromatic Pd2 complex 3 as well Hückel antiaromatic 2. This method can be applied to other expanded porphyrins and Group 10 metal ions. The aromatic/antiaromatic character was supported by NMR spectrscopy, NICS calculation, two-photon absorption measurements. Supporting information for this article is available on WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704407_s.pdf or from author. Please note: publisher not...
Abstract Curved π -conjugated molecules have attracted considerable interest because of the unique properties originating from their curved surface. However, synthesis such distorted requires harsh conditions, which hamper easy access to heteroatom-containing systems. Here we report a π-extended azacorannulene with nitrogen in its centre. The oxidation 9-aminophenanthrene provides tetrabenzocarbazole, is converted azabuckybowl through palladium-catalysed intramolecular coupling....
Synthesis, properties, and functions of bowl-shaped pi-conjugated molecules including a hetero atom-doped system are reviewed.
Small is beautiful: A ring-contracted sister of porphyrin, norcorrole, has been synthesized efficiently as a stable molecule by nickel-templated strategy. The norcorrole complex but exhibits distinct antiaromatic character according to the Hückel rule. Oxidation provides an aromatic oxacorrole complex. Detailed facts importance specialist readers are published ”Supporting Information”. Such documents peer-reviewed, not copy-edited or typeset. They made available submitted authors. Please...
meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism single-crystal X-ray diffraction analysis. All of these data consistently indicate that in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Möbius conformations with distinct aromaticities, a small contribution from planar rectangular conformation antiaromatic...
An aqueous biphasic reaction system enables the direct use of allyl alcohol in Tsuji−Trost without help any activating reagents for alcohol. The conditions are neutral to basic, allowing amines as nucleophile. Theoretical calculations have elucidated importance hydration hydroxy group smooth generation π-allylpalladium species.
Oxidation of a directly meso-meso linked cyclic porphyrin tetramer 2 gave sheet 3. The symmetric square structure 3 is indicated by its simple 1H NMR spectrum that exhibits only two signals for the beta-protons. absorption displays characteristic Soret-like broad bands and weak Q-bands, magnetic circular dichroism (MCD) negative Faraday A term at 762 nm band as rare case, indicating transition from nondegenerate level to degenerate level. slightly longer S1-state (1.1 ps) smaller TPA cross...
Halogen−magnesium exchange of various aryl halides is achieved with a magnesium ate complex at low temperatures. Tributylmagnesate (nBu3MgLi) induces facile iodine−magnesium −78 °C. Dibutylisopropylmagnesate (iPrnBu2MgLi) more reactive than nBu3MgLi, and this reagent accomplishes selective bromine−magnesium This procedure utilized for the preparation polyfunctionalized arylmagnesium species. The alkenyl using method proceeds retention configuration double bond.
Triethylborane-induced atom-transfer radical cyclization of iodo acetals and iodoacetates in water is described. Radical acetal proceeded smoothly both aqueous methanol water. Atom-transfer allyl iodoacetate (3a) much more efficient than benzene or hexane. For instance, treatment 3a with triethylborane hexane at room temperature did not yield the desired lactone. In contrast, cyclized yielded corresponding γ-lactone high yield. The remarkable solvent effect was observed this reaction,...
Abstract Organomagnesium compounds are among the most useful organometallic reagents in organic synthesis. Besides their classical nucleophilic reactions to carbonyl compounds, Grignard gain versatile reactivity when combined with various transition metal salts. In this article, we review mainly our own studies on manganese‐, iron‐, chromium‐, and cobalt‐catalyzed carbon−carbon bond formation using reagents. Other closely related research field is also discussed. (© Wiley‐VCH Verlag GmbH...
Highly regioselective borylation of 5,15-diaryl- and 5,10,15-triarylporphyrins has been achieved by the reaction with bis(pinacolato)diborane under iridium catalysis. Borylated porphyrins are a useful building block for constructing porphyrin arrays, hence offering an effective route to β-functionalized porphyrins.
A porphyrin nanobarrel, 1, that can encapsulate C(60) effectively was prepared via a concise coupling route. The structures of both 1 and C(60)@1 were confirmed by single-crystal X-ray diffraction analysis.
Although aromatic compounds occupy a central position in organic chemistry, antiaromatic have demonstrated little practical utility. Herein we report the application of an compound as electrode-active material rechargeable batteries. The performance dimesityl-substituted norcorrole nickel(II) complex (NiNC) cathode-active was examined with Li metal anode. A maximum discharge capacity about 207 mAhg(-1) maintained after 100 charge/discharge cycles. Moreover, bipolar redox property NiNC...
Treatment of a meso-arylboron dipyrrin (BODIPY) with NBS provides mono- and dibrominated BODIPYs at the 2- 6-positions in excellent yields high regioselectivity. Brominated products can be employed as nice building block for synthesis variety BODIPY derivatives through Suzuki–Miyaura coupling. Because lack substituents 1,3,5,7-positions, directly β–β-linked dimer exhibits completely coplanar conformation units, offering effective π-conjugation.
A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the β-position unit. The extended π-system fused induces near-infrared (NIR) absorption and strong π-π interactions in solid state. These features are beneficial for application dye as functional material. demonstrated to exhibit photocurrent conversion ability on basis its n-type semiconducting property.
The development of porphyrin synthesis by means transition metal-catalyzed reactions is explored in this feature article. Porphyrins have been receiving much attention a wide area chemistry as functional dyes, non-linear optical materials, ligands for variety metals, structural motifs supramolecules, and so forth. However, they merely recognized reaction substrate transformations. Recently, application such new methodologies to has proven be very powerful create types porphyrinic compounds,...
Which way to go: The product distribution in the efficient oxidation of 2-aminoanthracene derivatives pyrazine- and pyrrole-fused bisanthracenes can be controlled by additives (see scheme; TFA=trifluoroacetic acid, DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone). dimer regarded as an aza[7]helicene with a stable helical conformation. Detailed facts importance specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made...
Verwickelt: Metallierung des [36]Octaphyrins 1 lieferte den Möbius-aromatischen Pd2-Komplex 3 sowie Hückel-antiaromatischen 2. Die Synthesemethode kann auf andere Porphyrine und Metallionen der Gruppe 10 übertragen werden. Der aromatische/antiaromatische Charakter wurde durch NMR-Spektroskopie, NICS-Rechnungen Zweiphotonenabsorptionsmessungen bestätigt. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2008/z704407_s.pdf or from...
Treatment of perylene bisimide (PBI) with various arylboronates in the presence a ruthenium catalyst provides tetraarylated PBIs at 2,5,8,11-positions good yields perfect regioselectivity. The electronic nature introduced aryl substituents has significant impact on their optical and properties. This protocol been applied to synthesis water-soluble emissive PBI derivative.
Abstract Aromaticity is a key concept in organic chemistry. Even though this has already been theoretically extrapolated to three dimensions, it usually still remains restricted planar molecules chemistry textbooks. Stacking of antiaromatic π-systems proposed induce three-dimensional aromaticity as result strong frontier orbital interactions. However, experimental evidence support prediction elusive so far. Here we report that close stacking porphyrins diminishes their inherent...
We designed and synthesized molecular tweezers consisting of nitrogen-embedded buckybowl subunits. The judicious choice the covalent linkers modulated their binding strength with C60 or C70 in solution. Titration studies by optical 1H NMR analyses revealed a 1:1 composition resulting complexes. X-ray diffraction analysis elucidated solid-state structures, which two azabuckybowl units surround one fullerene molecule. large association constants stabilize complexes toward redox reactions...
Abstract Aromaticity is a fundamental concept in chemistry. It described by Hückel’s rule that states cyclic planar π-system aromatic when it shares 4 n +2 π-electrons and antiaromatic possesses π-electrons. Antiaromatic compounds are predicted to exhibit remarkable charge transport properties high redox activities. However, has so far only been possible measure with reduced aromaticity but not species due their energetic instability. Here, we address these issues investigating the...
Abstract Understanding of interactions among molecules is essential to elucidate the binding pharmaceuticals on receptors, mechanism protein folding and self-assembling organic molecules. While between two aromatic have been examined extensively, little known about antiaromatic Theoretical investigations predicted that should be stabilized when they stack with each other by attractive intermolecular interactions. Here, we report synthesis a cyclophane, in which porphyrin moieties adopt...
The reversible formation of σ-bonds between organic radicals has been widely investigated. However, reports on the σ-dimers from delocalized π-radical cations are scarce. Herein, we report σ-dimerization behavior a bowl-shaped cation generated nitrogen-embedded buckybowl, both in crystalline state and solution. detailed structure σ-dimer was determined by single-crystal X-ray diffraction analysis. monomeric radical exists predominantly solution at room temperature, while dimerization occurs...