Shinichi Itsuno

Find an error

Name:

Organization: Toyohashi University of Technology

Department: Department of Environmental & Life Sciences

Title:

TOPICS

Polymer

sustainable polymer sustainable polymer

Organic Chemistry

Asymmetric Synthesis Organocatalysis Diels Alder Reaction Hydrogenation

Chemicals
References

Synthesis of Chiral Polyamides Containing an (R,R)-1,2-Diphenylethylenediamine Monosulfonamide Structure and Their Application to Asymmetric Transfer Hydrogenation Catalysis

Co-reporter: Dr. Shinichi Itsuno;Shotaro Takahashi

ChemCatChem 2017 Volume 9(Issue 3) pp:385-388

Publication Date(Web):2017/02/06

DOI:10.1002/cctc.201601220

AbstractA chiral main-chain polyamide containing an (R,R)-1,2-diphenylethylenediamine monotoluenesulfonamide (TsDPEN) repeating unit was prepared. Polycondensation of dicarboxylic acid dichloride with the chiral bisaniline of N-tert-butoxycarbonyl-protected TsDPEN was successful and afforded a chiral polyamide with a TsDPEN repeating unit as the chiral ligand structure. Treatment of the main-chain polymer chiral ligand with transition-metal complexes, such as [IrCl2Cp*]2 (Cp*=η5-pentamethylcyclopentadienyl), [RhCl2Cp*]2, and [RuCl2(p-cymene)]2, afforded polymer chiral metal complexes. Asymmetric transfer hydrogenation of a cyclic sulfonamide was efficiently catalyzed by the chiral TsDPEN polymer–metal complex to give an optically active cyclic sulfonylamine with quantitative conversion and high enantioselectivity. The polymer catalyst was easily recovered from the reaction mixture and reused several times without any loss in catalytic activity or enantioselectivity.

Synthesis of cinchona alkaloid squaramide polymers as bifunctional chiral organocatalysts for the enantioselective michael addition of β-ketoesters to nitroolefins

Co-reporter:Mohammad Shahid Ullah, Shinichi Itsuno

Molecular Catalysis 2017 Volume 438(Volume 438) pp:

Publication Date(Web):1 September 2017

DOI:10.1016/j.mcat.2017.06.010

•Synthesis of novel chiral polymers containing cinchona-based squaramide.•Application of Mizoroki-Heck reaction for the preparation of the chiral polymers.•High catalytic activity of the chiral polymers in asymmetric Michael reaction.•Recyclability of chiral polymers.Novel chiral polymers containing cinchona-based squaramides in their main chain structure were designed. We synthesized chiral squaramides bearing two cinchona moieties, which contain double bonds. Repeated Mizoroki-Heck reactions between the double bonds of the cinchona-based squaramide and aromatic diiodides proceeded smoothly to give cinchona squaramide chiral polymers. The catalytic activity of the chiral polymers was subsequently investigated. The asymmetric Michael addition of β-ketoesters to nitroolefins was successfully catalyzed by the polymeric organocatalysts to give the corresponding Michael adducts in good yields and excellent enantioselectivities of up to 99% ee. As the polymeric catalysts were insoluble in commonly used organic solvents, they were easily recovered from the reaction mixture and reused for further reaction without any loss of catalytic activity.Download full-size image

Inside Cover: Synthesis of Chiral Polyamides Containing an (R,R)-1,2-Diphenylethylenediamine Monosulfonamide Structure and Their Application to Asymmetric Transfer Hydrogenation Catalysis (ChemCatChem 3/2017)

Co-reporter: Dr. Shinichi Itsuno;Shotaro Takahashi

ChemCatChem 2017 Volume 9(Issue 3) pp:375-375

Publication Date(Web):2017/02/06

DOI:10.1002/cctc.201700122

The Cover shows a chiral main-chain polyamide containing a (R,R)-1,2-diphenylethylenediamine monotoluenesulfonamide (TsDPEN) repeat unit as the chiral ligand structure.In their Communication, S. Itsuno et al. demonstrate the synthesis of main-chain TsDPEN polymers by polycondensation of dicarboxylic acid dichloride with the chiral bisaniline of N-Boc-protected TsDPEN for the first time. Treatment of the chiral polymer ligand with transition metal complexes afforded polymer chiral metal complexes. Asymmetric transfer hydrogenation of a cyclic sulfonamide was efficiently catalyzed by the chiral polymer–metal complex, giving an optically active cyclic sulfonylamine with high enantioselectivities. The polymer catalyst was easily recovered from the reaction mixture and reused several times without any loss in catalytic activity and enantioselectivity. More information can be found in the Communication by S. Itsuno et al. on page 385 in Issue 3, 2017 (DOI: 10.1002/cctc.201601220).

Synthesis of cinchona alkaloid sulfonamide polymers as sustainable catalysts for the enantioselective desymmetrization of cyclic anhydrides

Co-reporter:Shohei Takata, Yuta Endo, Mohammad Shahid Ullah and Shinichi Itsuno

RSC Advances 2016 vol. 6(Issue 76) pp:72300-72305

Publication Date(Web):25 Jul 2016

DOI:10.1039/C6RA14535C

The Mizoroki–Heck polymerization of cinchona-based sulfonamide dimers and aromatic diiodides was investigated in the presence of a palladium catalyst, to obtain chiral polymers in high yields. An iodobenzenesulfonamide derivative of a cinchona alkaloid was also polymerized via self-polycondensation under the same reaction conditions. The catalytic activities of these chiral polymers were examined by using them as catalysts in the enantioselective desymmetrization of cyclic anhydrides.

Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10,11-didehydrogenated cinchonidinium salt

Co-reporter:Md. Mehadi Hassan;Naoki Haraguchi

Journal of Polymer Science Part A: Polymer Chemistry 2016 Volume 54( Issue 5) pp:621-627

Publication Date(Web):

DOI:10.1002/pola.27905

ABSTRACT

Since few examples of 10,11-didehydrogenated (3-ethynyl) cinchona alkaloids have been utilized as organocatalysts in asymmetric reaction, we synthesized 10,11-didehydrogenated cinchonidine. The 3-vinyl group of cinchonidine was transformed into a 3-ethynyl functionality. Based on the resulting 10,11-didehydrogenated cinchonidine, the corresponding quaternary ammonium salt and its dimers were prepared. The ion-exchange reaction between the quaternary ammonium salt and sodium sulfonate produced the quaternary ammonium sulfonate as a stable ionic compound. Chiral ionic polymers were then synthesized by the ion-exchange polymerization of the 10,11-didehydrogenated cinchonidinium salt dimer and a disulfonate. The chiral ionic polymers were found to be capable of efficiently catalyzing the asymmetric alkylation of N-(diphenylmethylene)glycine tert-butyl ester. The enantioselectivities obtained with the polymeric catalysts were higher than those obtained with the corresponding monomeric catalyst. Dimers of 10,11-didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N-(diphenylmethylen)glycine tert-butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 621–627

Synthesis of Chiral Polyethers Containing Imidazolidinone Repeating Units and Application as Catalyst in Asymmetric DielsAlder Reaction

Co-reporter:Shinichi Itsuno;Tatsuaki Oonami;Nagisa Takenaka ;Naoki Haraguchi

Advanced Synthesis & Catalysis 2015 Volume 357( Issue 18) pp:3995-4002

Publication Date(Web):

DOI:10.1002/adsc.201500539

Polymer-immobilized chiral catalysts

Co-reporter:Shinichi Itsuno and Md. Mehadi Hassan

RSC Advances 2014 vol. 4(Issue 94) pp:52023-52043

Publication Date(Web):09 Oct 2014

DOI:10.1039/C4RA09561H

Polymer immobilization of chiral catalysts has progressed extensively over the past years. Recent intensive development of chiral organocatalysts resulted in the identification of numerous highly active catalysts, which are, however, still far less effective than transition metal catalysts. Separation of relatively large amounts of organocatalysts from the reaction mixture causes problems during product isolation. In the case of chirally modified metal catalysts, recovery of valuable metal species and suppression of metal leaching are perpetually important requirements in the design of environmentally friendly chemical processes. Various types of chiral organocatalysts and metal catalysts have been immobilized as pendant groups onto the side chains of polymer supports. Another important polymer immobilization technique is the incorporation of a chiral catalyst into its main chain, with several types of chiral catalyst monomers having been copolymerized with achiral monomers for their production. Recently, the synthesis of chiral main-chain polymeric catalysts has progressed extensively. Moreover, many examples of polymer-immobilized catalysts exhibit higher enantioselectivities in comparison to those of the corresponding low-molecular-weight catalysts. The development of these polymer-immobilized chiral catalysts, which have largely been reported in the last five years, is reviewed in this article.

Synthesis of cinchonidinium salts containing sulfonamide functionalities and their catalytic activity in asymmetric alkylation reactions

Co-reporter:Shinichi Itsuno, Shunya Yamamoto, Shohei Takata

Tetrahedron Letters 2014 Volume 55(Issue 44) pp:6117-6120

Publication Date(Web):29 October 2014

DOI:10.1016/j.tetlet.2014.09.052

Various kinds of 4-(bromomethyl)benzenesulfonamides were prepared as quaternization reagent of cinchonidine. Cinchonidinium salts obtained from the quaternization of cinchonidine with 4-(bromomethyl)benzenesulfonamide showed highly enantioselective catalytic activity in the asymmetric benzylation of N-(diphenylmethylene)glycine tert-butyl ester. The corresponding phenylalanine derivative was obtained in high yield with a high level of enantioselectivity, up to 98% ee.

Synthesis of polymer-immobilized TsDPEN ligand and its application in asymmetric transfer hydrogenation of cyclic sulfonimine

Co-reporter:Haruki Sugie, Yosuke Hashimoto, Naoki Haraguchi, Shinichi Itsuno

Journal of Organometallic Chemistry 2014 Volume 751() pp:711-716

Publication Date(Web):1 February 2014

DOI:10.1016/j.jorganchem.2013.09.008

•The polymer-immobilized chiral N-sulfonylated diamine ligands were prepared.•The polymeric chiral Ru complexes were used as catalyst for asymmetric transfer hydrogenation.•Hydrophobic polymeric catalysts performed very well in organic solvent such as CH2Cl2.•Amphiphilic polymeric catalysts were efficiently used for the same asymmetric reaction in water.Crosslinked polymers containing chiral N-sulfonylated diamine (TsDPEN) structure were synthesized by radical polymerization of chiral N1-(4-vinylbenzenesulfonyl)-1,2-diphenylethylene-1,2-diamine, divinylbenzene and achiral vinyl monomer. The polymer-immobilized chiral complex was prepared from the polymeric TsDPEN with ruthenium dichloride p-cymene. Asymmetric transfer hydrogenation of cyclic sulfonimine was performed using the polymer-immobilized TsDPEN–Ru (II) complex. The hydrophobic–hydrophilic balance of the polymers was tuned by means of the incorporation of the achiral vinyl monomers, which strongly influenced on the catalytic activity of the polymeric catalyst. In most cases the amphiphilic polymer-immobilized chiral catalysts are highly active in the asymmetric transfer hydrogenation. Enantioenriched sultam with up to 98% ee was obtained by using polymer-immobilized chiral catalysts containing quaternary ammonium salt in CH2Cl2. Some of the polymer-immobilized chiral catalysts containing quaternary ammonium salt were successfully used in water. Up to 95% ee was obtained by using the polymeric catalyst in water. Most of the quaternized polymeric catalysts showed sufficient reactivity and higher enantioselectivities compared with that of low-molecular-weight catalyst in water.Amphiphilic polymer-immobilized chiral Ru complexes displayed excellent catalytic activity in asymmetric transfer hydrogenation of cyclic imines both in water and organic solvent.

Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

Co-reporter:Shinichi Itsuno;Yosuke Hashimoto ;Naoki Haraguchi

Journal of Polymer Science Part A: Polymer Chemistry 2014 Volume 52( Issue 21) pp:3037-3044

Publication Date(Web):

DOI:10.1002/pola.27351

ABSTRACT

This article details the enantioselective catalytic performance of crosslinked, polymer immobilized, Ir-based, chiral complexes for transfer hydrogenation of cyclic imines to chiral amines. Polymerization of the achiral vinyl monomer, divinylbenzene, and a polymerizable chiral 1,2-diamine monosulfonamide ligand followed by complexation with [IrCl₂Cp*]₂ affords the crosslinked polymeric chiral complex, which can be successfully applied to asymmetric transfer hydrogenation of cyclic imines. Polymeric catalysts prepared from amphiphilic achiral monomers have high catalytic activity in the reaction and can be used both in organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity (up to 98% ee). The asymmetric reaction allows for reuse of the heterogeneous catalyst without any loss in activity or enantioselectivity over several runs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3037–3044

Synthesis of Cinchona Alkaloid-Derived Chiral Polymers by Mizoroki–Heck Polymerization and Their Application to Asymmetric Catalysis

Co-reporter:Md. Masud Parvez, Naoki Haraguchi, and Shinichi Itsuno

Macromolecules 2014 Volume 47(Issue 6) pp:1922-1928

Publication Date(Web):March 11, 2014

DOI:10.1021/ma5001018

To facilitate the asymmetric catalysis process, we designed novel polymeric chiral catalysts. Since quaternary ammonium salts of cinchona alkaloid derivatives show efficient catalytic activity in various asymmetric transformations, we have synthesized novel chiral polymer catalysts containing cinchonidinium moieties in the main chain of the polymer. Repetitive Mizoroki–Heck coupling reactions between the cinchona alkaloid-derived dimer and diiodide afforded the chiral polymer catalysts, which were subsequently used as catalysts in asymmetric benzylation reactions to yield the corresponding phenylalanine derivatives in higher yields and levels of enantioselectivity than can be obtained with a monomeric catalyst. Because of the insolubility of the polymeric catalysts, they were easily recovered from the reaction mixture and reused several times.

Synthesis of chiral polymers containing thioetherified cinchonidinium repeating units and their application to asymmetric catalysis

Co-reporter:Md. Robiul Islam, Parbhej Ahamed, Naoki Haraguchi, Shinichi Itsuno

Tetrahedron: Asymmetry 2014 Volume 25(18–19) pp:1309-1315

Publication Date(Web):15 October 2014

DOI:10.1016/j.tetasy.2014.08.013

A thiol-ene reaction of dithiol and two equivalents of cinchonidine afforded a thioetherified cinchonidine dimer. The dimer was treated with benzyl bromide to give a quaternary ammonium dimer. An ion exchange reaction of the cinchonidinium dimer and disodium disulfonate gave polymers containing chiral quaternary ammonium repeating units in their main-chain structures. Another type of chiral polymer was synthesized by quaternization polymerization. Repeated quaternization reactions between the thioetherified cinchonidine dimer and dihalides yielded chiral polymers containing cinchonidinium structures in their main chains. Both of these chiral polymers were successfully used as catalysts for the asymmetric alkylation of N-diphenylmethylene glycine tert-butyl ester. The chiral cinchonidinium polymers explored in this study showed excellent catalytic activity in asymmetric alkylation reactions and were reused several times without loss of activity.(R)-((1S,2S,4S,5R)-5-(2-(tert-Butylthio)ethyl)quinuclidin-2-yl)(quinolin-4-yl)methanolC23H32N2OS[α]D25 = −63.9 (c 1.0, DMSO)Source of chirality: CinchonidineAbsolute configuration: (R)-(1S,2S,4S,5R)(1S,2S,4S,5R)-1-Benzyl-5-(2-(tert-butylthio)ethyl)-2-((R)-hydroxy(quinolin-4-yl)methyl)quinuclidin-1-ium bromideC30H39BrN2OS[α]D25 = −125.3 (c 1.0, DMSO)Source of chirality: CinchonidineAbsolute configuration: (1S,2S,4S,5R)(1R,1′R)-((2′R)-5,5′-((Hexane-1,6-diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis(quinuclidine-5,2-diyl))bis(quinolin-4-ylmethanol)C44H58N4O2S2[α]D25 = −57.6 (c 1.0, DMSO)Source of chirality: CinchonidineAbsolute configuration: (1R,1′R)(2′R)(1R,1′R)-((2′R)-5,5′-(((1,4-Phenylenebis(methylene))bis(sulfanediyl))bis(ethane-2,1-diyl))bis(quinuclidine-5,2-diyl))bis(quinolin-4-ylmethanol)C46H54N4O2S2[α]D25 = −35.4 (c 1.0, DMSO)Source of chirality: CinchonidineAbsolute configuration: (1R,1′R)-((2′R)1-Benzyl-5-(2-((6-((2-((6R)-1-benzyl-6-((R)-hydroxy(quinolin-4-yl)methyl)quinuclidin-1-ium-3-yl)ethyl)thio)hexyl)thio)ethyl)-2-((R)-hydroxy(quinolin-4-yl)methyl)quinuclidin-1-ium bromideC58H72Br2N4O2S2[α]D25 = −105.9 (c 1.0, DMSO)Source of chirality: Cinchonidine1-Benzyl-5-(2-((4-(((2-((6R)-1-benzyl-6-((R)-hydroxy(quinolin-4-yl)methyl)quinuclidin-1-ium-3-yl)ethyl)thio)methyl)benzyl)thio)ethyl)-2-((R)-hydroxy(quinolin-4-yl)methyl)quinuclidin-1-ium bromideC60H68Br2N4O2S2[α]D25 = −85.8 (c 1.0, DMSO)Source of chirality: Cinchonidine

Synthesis of chiral quaternary ammonium polymers for asymmetric organocatalysis application

Co-reporter:Parbhej Ahamed, Md. Aminul Haque, Mikiya Ishimoto, Md. Masud Parvez, Naoki Haraguchi, Shinichi Itsuno

Tetrahedron 2013 69(19) pp: 3978-3983

Publication Date(Web):

DOI:10.1016/j.tet.2013.03.018

Molecular design of chiral quaternary ammonium polymers for asymmetric catalysis applications

Co-reporter:Md. Masud Parvez, Naoki Haraguchi and Shinichi Itsuno

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 14) pp:2870-2877

Publication Date(Web):07 Feb 2012

DOI:10.1039/C2OB06909A

Repeated reaction between a chiral quaternary ammonium dimer and disodium disulfonate gave a chiral ionic polymer, which showed excellent catalytic activity in the asymmetric benzylation of N-diphenylmethylene glycine tert-butyl ester.

Polymeric chiral organocatalysts

Co-reporter:Shinichi Itsuno, Md. Masud Parvez and Naoki Haraguchi

Polymer Chemistry 2011 vol. 2(Issue 9) pp:1942-1949

Publication Date(Web):12 May 2011

DOI:10.1039/C1PY00083G

Incorporation of a chiral quaternary ammonium salt into a polymer allows for the preparation of a polymeric chiral organocatalyst that can be utilized in various asymmetric transformations in organic synthesis. Chiral quaternary ammonium salts are among the most important and frequently used organocatalysts. There is an increased focus on new strategies for the incorporation of chiral quaternary ammonium salts into polymers. We have found that ionic-bond formation between a quaternary nitrogen and a sulfonate anion can be successfully used to link an organocatalyst to a polymer support. Stable ionic bonds formed by quaternary ammonium sulfonate can also be used in main-chain chiral polymer synthesis. The potential applications of the ionic-bond formation method in the construction of new chiral macromolecular architectures are discussed herein.

Molecular design of chiral quaternary ammonium polymers for asymmetric catalysis applications

Co-reporter:Md. Masud Parvez, Naoki Haraguchi and Shinichi Itsuno

Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 14) pp:NaN2877-2877

Publication Date(Web):2012/02/07

DOI:10.1039/C2OB06909A