A5026983143- Synthesis and Properties of Aromatic Compounds
- Catalytic C–H Functionalization Methods
- Advanced Polymer Synthesis and Characterization
- Supramolecular Self-Assembly in Materials
- Catalytic Cross-Coupling Reactions
- Organoboron and organosilicon chemistry
- Synthesis and properties of polymers
- Photopolymerization techniques and applications
- Asymmetric Hydrogenation and Catalysis
- Supramolecular Chemistry and Complexes
- Polydiacetylene-based materials and applications
- biodegradable polymer synthesis and properties
- Various Chemistry Research Topics
- Covalent Organic Framework Applications
- Chemical Synthesis and Reactions
- Synthetic Organic Chemistry Methods
- Photochromic and Fluorescence Chemistry
- Silicone and Siloxane Chemistry
- Organic Electronics and Photovoltaics
- Advanced Synthetic Organic Chemistry
- Axial and Atropisomeric Chirality Synthesis
- Analytical Chemistry and Chromatography
- Membrane Separation and Gas Transport
- Molecular spectroscopy and chirality
- Carbon dioxide utilization in catalysis
Kitami Institute of Technology
2012-2022
University of Fukui
2004-2019
Niigata University
2008-2012
Center for Research and Interdisciplinarity
2010
A novel, highly selective photocyclic aromatization (SCAT) of π-conjugated polymers from phenylacetylene having two hydroxyl groups to exclusively yield a 1,3,5-trisubstituted benzene derivative was developed, and its success confirmed by (1)H NMR, GPC, TOF-MS. The SCAT reaction has many unique characteristics. (1) It is quantitative reaction: it gave only the corresponding cyclic trimer, i.e., derivative, quantitatively (100%). No byproducts were produced under best conditions. (2) an...
One of the authors discovered helix-sense-selective polymerization (HSSP) an achiral substituted phenylacetylene which has two hydroxymethyl groups and a relatively hydrophobic substituent by using chiral catalytic system in 2003. The one-handed helicity is stable static nonpolar solvents because it maintained intramolecular hydrogen bonds. Since resulting polymer extremely tight its main chain, shows many interesting unusual properties including highly selective photocyclic aromatization...
To develop new phenylacetylene monomers more suitable for helix-sense-selective polymerization (HSSP) we reported previously and to improve the efficiency of HSSP membrane performance resulting polymers, novel phenylacetylenes having a flexible oligosiloxanyl group (SnBDHPA) together with other related three series were synthesized polymerized by using chiral catalytic system enantioselectivity in permeation membranes from polymers examined. SnBDHPA was most CD absorptions (G values)...
Abstract 4‐Alkyloxy‐3,5‐bis(hydroxymethyl)phenylacetylenes with eight types of alkyl groups were synthesized and polymerized a chiral catalytic system. We found that the length played very important role in achieving helix‐sense‐selective polymerization. Five polymerizations achieved resulting polymers whose chain was longer than six. think ‐ prevented from becoming insoluble by forming inter molecular hydrogen bonds between hydroxyl groups, stabilized their one‐handed helical structure...
Abstract The intermolecular dehydrogenative coupling of 1,1,1,3,5,5,5-heptamethyltrisiloxane with aromatic compounds such as aryloxazolines and arylimines in the presence a catalytic amount [RuCl2(p-cymene)]2 gave corresponding ortho-silylated products good yields.
Three novel chiral phenylacetylenes having an octyloxyethanolamine residue derived from a l-aminoalcohol and two hydroxymethyl groups were synthesized polymerized by achiral catalysts ((nbd)Rh+[η6-(C6H5)B−(C6H5)3] [Rh(nbd)Cl]2/triethylamine (TEA)) catalytic system ([Rh(nbd)Cl]2/(S)- or (R)-phenylethylamine ((S)- (R)-PEA)). All of the resulting polymers showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had excess one-handed helical backbones. Positive...
Abstract The ruthenium‐catalyzed dehydrogenative borylation of 2‐arylpyridines with pinacolborane took place at ortho ‐positions the benzene ring. Density functional theory calculations and kinetic isotope effect experiments suggest that catalytic cycle should involve oxidative addition CH bond, rate‐determining σ‐bond metathesis ruthenium hydride complex, reductive elimination CB bond.
ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication the EditorNEXTTwo Modes of Asymmetric Polymerization Phenylacetylene Having a l-Valinol Residue and Two Hydroxy GroupsHongge Jia†, Masahiro Teraguchi†‡§, Toshiki Aoki*†‡∥, Yunosuke Abe†, Takashi Kaneko‡§, Shingo Hadano§∥, Takeshi Namikoshi§∥, Edy Marwanta§∥View Author Information Department Chemistry Chemical Engineering, Graduate School Science Technology, Center for Education Research on Environmental Materials...
Abstract The Ru‐catalyzed dehydrogenative silylation of 2‐alkyloxazolines with 1,1,1,3,5,5,5‐heptamethyltrisiloxane took place site‐selectively at methyl C(sp 3 )−H bonds located γ to the nitrogen atom oxazolyl groups. Pyridine and pyrazole rings could also be used as a directing group. A catalytic mechanism based upon successive σ‐bond metathesis is proposed.
Abstract The ruthenium‐catalyzed dehydrogenative silylation of benzamides with 1,1,1,3,5,5,5‐heptamethyltrisiloxane took place at ortho ‐positions the benzene ring. Several containing both electron‐donating and electron‐withdrawing groups could be used in this silylation. Density functional theory (DFT) calculations kinetic isotope effect experiments suggest that catalytic cycle should involve CSi bond formation as rate‐determining step. magnified image
The intramolecular dehydrogenative cyclization of 2-(dialkylsilyl)biaryls proceeded in the presence a catalytic amount platinum(II) chloride and potassium tris(3,5-dimethyl-1-pyrazolyl)borohydride to give good yields corresponding dibenzosilole derivatives.
The polymerizations of vinyl ethers with a tricyclodecane or tricyclodecene unit (1, 2, and 3) the HCl/ZnCl2 initiating system in toluene at −30 °C proceeded living manner to give high molecular-weight polymers controlled molecular weights narrow weight distributions. Tg's poly(1) poly(2) reached ∼100 °C, whereas Tg poly(3) was lower than those poly(2), but still much higher room temperature. These results show that rigid tricyclic groups side chains effectively elevate poly(vinyl ethers)s.
A one‐handed helical cis‐cisoidal polyphenylacetylene ( P ) is successfully synthesized by an asymmetric‐induced polymerization of a chiral‐substituted phenylacetylene having two hydroxymethyl groups. Quantitative photocyclic aromatization in membrane‐state followed situ removal the chiral substituents affords supramolecular polymer membrane corresponding cyclic trimer T) with no substituents. The original helicity precursor transmitted to resulting supramolecular de ‐ T . Both hydrogen...
Abstract To study the possibility of living cationic polymerization vinyl ethers with a urethane group, 4‐vinyloxybutyl n ‐butylcarbamate ( 1 ) and phenylcarbamate 2 were polymerized hydrogen chloride/zinc chloride initiating system in methylene solvent at −30 °C ([monomer] 0 = 0.30 M, [HCl] /[ZnCl ] 5.0/2.0 mM). The was very slow gave only low‐molecular‐weight polymers number‐average molecular weight M about 2000 even 100% monomer conversion. structural analysis products showed occurrence...
Abstract The cross-coupling of aryl arenesulfonates with dialkoxyboranes proceeded in the presence Bu4NI and a catalytic amount [Pd(dba)2]/1,1′-bis(di-tert-butylphosphano)ferrocene, giving good yields corresponding arylboronates. protocols tolerate wide range functional groups, including ester, nitrile, ketone.
The sequential living cationic polymerization of 8-vinyloxytricyclo[5.2.1.02, 6]decane (TCDVE) and n-butyl vinyl ether (NBVE) afforded the A-B-A type triblock copolymer, poly(TCDVE)-block-poly(NBVE)-block-poly(TCDVE). Although composed solely poly- (vinyl ether) main chains, copolymer formed a thermoplastic elastomer with microphase-separated structure. [Color figure can be viewed in online issue, which is available at www.interscience.wiley.com.] Vinyl one representative monomers...
Electron-donating or ortho substituted aromatic bromides give low yields compared to the corresponding iodides (IIa) and (IId).