Takashi Ooi

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Organization: Nagoya University

Department: Department of Applied Chemistry, Graduate School of Engineering

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Organic Chemistry

Asymmetric Synthesis Organocatalysis Cyanation

Chemicals
References

Acridinium Betaine as a Single-Electron-Transfer Catalyst: Design and Application to Dimerization of Oxindoles

Co-reporter:Daisuke Uraguchi, Masahiro Torii, and Takashi Ooi

ACS Catalysis April 7, 2017 Volume 7(Issue 4) pp:2765-2765

Publication Date(Web):March 16, 2017

DOI:10.1021/acscatal.7b00265

An intramolecular ion-pairing acridinium phenoxide possessing a redox-active component and a basic site within a single molecular framework is developed. The potential of the acridinium betaine as a chemical redox catalyst is demonstrated by its application to the homodimerization of 3-aryl oxindoles, which proceeds through proton-coupled electron-transfer pathway. Analysis of the kinetic profile has provided important clues to understand the reaction mechanism.Keywords: betaine; chemical redox; organocatalysis; oxindole; proton-coupled electron transfer;

Unique site-selectivity control in asymmetric Michael addition of azlactone to alkenyl dienyl ketones enabled by P-spiro chiral iminophosphorane catalysis

Co-reporter:Ken Yoshioka;Kohei Yamada;Daisuke Uraguchi

Chemical Communications 2017 vol. 53(Issue 40) pp:5495-5498

Publication Date(Web):2017/05/17

DOI:10.1039/C7CC01715D

A highly regio-, diastereo-, and enantioselective 1,6-addition of azlactone to various alkenyl dienyl ketones has been achieved under P-spiro chiral triaminoiminophosphorane catalysis. This site-selectivity control relies on the distinct ability of the conjugate acids of iminophosphoranes, aminophosphonium ions, to precisely differentiate between the three electrophilic reaction sites of alkenyl dienyl ketones, which is further demonstrated by the discriminative asymmetric 1,6-addition of azlactone to dienyl ketones, leaving the coexisting alkenyl ketone intact.

Independence from the Sequence of Single-Electron Transfer of Photoredox Process in Redox-Neutral Asymmetric Bond-Forming Reaction

Co-reporter:Tomohito Kizu, Daisuke Uraguchi, and Takashi Ooi

The Journal of Organic Chemistry 2016 Volume 81(Issue 16) pp:6953-6958

Publication Date(Web):May 13, 2016

DOI:10.1021/acs.joc.6b00445

A catalytic cycle initiated by the oxidative quenching of the excited photosensitizer (Ir*(ppy)3) is established for the enantioselective coupling between (N-arylamino)methanes and (N-methanesulfonyl)aldimines catalyzed by Ir-based photosensitizer and a chiral (arylamino)phosphonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate under visible light irradiation. This achievement clearly demonstrates the insensitivity of this redox-neutral asymmetric reaction to the sequence of the key redox events involved in the synergistic catalysis.

Synergistic Catalysis of Ionic Brønsted Acid and Photosensitizer for a Redox Neutral Asymmetric α-Coupling of N-Arylaminomethanes with Aldimines

Co-reporter:Daisuke Uraguchi; Natsuko Kinoshita; Tomohito Kizu

Journal of the American Chemical Society 2015 Volume 137(Issue 43) pp:13768-13771

Publication Date(Web):October 11, 2015

DOI:10.1021/jacs.5b09329

A redox neutral, highly enantioselective coupling between N-arylaminomethanes and N-sulfonyl aldimines was developed by harnessing the efficient catalysis of P-spiro chiral arylaminophosphonium barfate and a transition-metal photosensitizer under visible light irradiation. This mode of synergistic catalysis provides a powerful strategy for controlling the bond-forming processes of reactive radical intermediates.

Enantioselective reductive multicomponent coupling reactions between isatins and aldehydes

Co-reporter:Matthew A. Horwitz, Naoya Tanaka, Takuya Yokosaka, Daisuke Uraguchi, Jeffrey S. Johnson and Takashi Ooi

Chemical Science 2015 vol. 6(Issue 11) pp:6086-6090

Publication Date(Web):30 Jul 2015

DOI:10.1039/C5SC02170G

A metal-free stereoselective reductive coupling reaction between isatins and aldehydes is reported. The reaction relies on commercial diethyl phosphite (∼€70 kg−1) as the stoichiometric reductant. Base-catalyzed Pudovik addition and phosphonate/phosphate rearrangement achieved polarity inversion on the isatin, and the derived carbanions were trapped by aldehydes with subsequent dialkoxyphosphinyl migration. Chiral iminophosphoranes were used as basic catalysts to achieve high diastereo- and enantioselectivities with excellent yields.

Vinylogy in nitronates: utilization of α-aryl conjugated nitroolefins as a nucleophile for a highly stereoselective aza-Henry reaction

Co-reporter:Keigo Oyaizu, Daisuke Uraguchi and Takashi Ooi

Chemical Communications 2015 vol. 51(Issue 21) pp:4437-4439

Publication Date(Web):03 Feb 2015

DOI:10.1039/C4CC10261D

The vinylogous reactivity of α,β-disubstituted nitroolefins was uncovered through the facile generation of the corresponding α-substituted vinylogous nitronates and their use in the development of a highly diastereo- and enantioselective aza-Henry reaction with N-Boc aldimines under the catalysis of chiral ammonium betaines. The novel vinylogous nitronates undergo stereoselective bond formation at the sterically encumbered α-position exclusively, allowing the construction of contiguous tertiary–quaternary stereogenic carbon centers.

Design of supramolecular chiral ligands for asymmetric metal catalysis

Co-reporter:Kohsuke Ohmatsu, Takashi Ooi

Tetrahedron Letters 2015 Volume 56(Issue 16) pp:2043-2048

Publication Date(Web):15 April 2015

DOI:10.1016/j.tetlet.2015.02.096

Three strategies for the development of supramolecular chiral ligands for asymmetric metal catalysis are outlined. The basic ideas, advantages, and examples of each strategy are described.Figure optionsDownload full-size imageDownload high-quality image (84 K)Download as PowerPoint slide

Chiral Ammonium Betaine-Catalyzed Highly Stereoselective Aza-Henry Reaction of -Aryl Nitromethanes with Aromatic N-Boc Imines

Co-reporter:Dr. Daisuke Uraguchi;Keigo Oyaizu;Haruhiro Noguchi;Dr. Takashi Ooi

Chemistry – An Asian Journal 2015 Volume 10( Issue 2) pp:334-337

Publication Date(Web):

DOI:10.1002/asia.201402943

Abstract

A highly stereoselective aza-Henry reaction of α-aryl nitromethanes with aromatic N-Boc imines was established by using C₁-symmetric chiral ammonium betaine as a bifunctional organic base catalyst. Various substituted aryl groups for both imines and nitromethanes were tolerated in the reaction, and a series of precursors for the synthesis of unsymmetrical anti-1,2-diaryl ethylenediamines was provided.

Inside Cover: Chiral Ammonium Betaine-Catalyzed Highly Stereoselective Aza-Henry Reaction of -Aryl Nitromethanes with Aromatic N-Boc Imines (Chem. Asian J. 2/2015)

Co-reporter:Dr. Daisuke Uraguchi;Keigo Oyaizu;Haruhiro Noguchi;Dr. Takashi Ooi

Chemistry – An Asian Journal 2015 Volume 10( Issue 2) pp:

Publication Date(Web):

DOI:10.1002/asia.201590001

Highly E-Selective and Enantioselective Michael Addition to Electron-Deficient Internal Alkynes Under Chiral Iminophosphorane Catalysis

Co-reporter:Dr. Daisuke Uraguchi;Kohei Yamada;Dr. Takashi Ooi

Angewandte Chemie 2015 Volume 127( Issue 34) pp:10092-10095

Publication Date(Web):

DOI:10.1002/ange.201503928

Abstract

A highly E-selective and enantioselective conjugate addition of 2-benzyloxythiazol-5(4H)-ones to β-substituted alkynyl N-acyl pyrazoles is achieved under the catalysis of a P-spiro chiral iminophosphorane. Simultaneous control of the newly generated central chirality and olefin geometry is possible with a wide array of the alkynyl Michael acceptors possessing different aromatic and aliphatic β-substituents, as well as the various α-amino acid-derived thiazolone nucleophiles. This protocol provides access to structurally diverse, optically active α-amino acids bearing a geometrically defined trisubstituted olefinic component at the α-position.

Highly E-Selective and Enantioselective Michael Addition to Electron-Deficient Internal Alkynes Under Chiral Iminophosphorane Catalysis

Co-reporter:Dr. Daisuke Uraguchi;Kohei Yamada;Dr. Takashi Ooi

Angewandte Chemie International Edition 2015 Volume 54( Issue 34) pp:9954-9957

Publication Date(Web):

DOI:10.1002/anie.201503928

Abstract

Palladium-Catalyzed Asymmetric [3 + 2] Cycloaddition of 5-Vinyloxazolidinones with Imines Using Chiral Ammonium-Phosphine Hybrid Ligand

Co-reporter:Kohsuke Ohmatsu, Shinya Kawai, Naomichi Imagawa, and Takashi Ooi

ACS Catalysis 2014 Volume 4(Issue 12) pp:4304

Publication Date(Web):October 24, 2014

DOI:10.1021/cs501369z

A palladium-catalyzed asymmetric [3 + 2] annulation reaction between racemic 5-vinyloxazolidinones and N-sulfonyl imines was established. Under the influence of the palladium complex with a chiral ammonium-phosphine hybrid ligand, the cycloaddition proceeded smoothly to yield imidazolidines bearing α-amino quaternary stereocenters in high yields with excellent diastereo- and enantioselectivities.Keywords: ammonium ion; asymmetric catalysis; cycloaddition; imidazolidine; palladium; phosphine

In situ generation of ion-paired chiral ligands: rapid identification of the optimal ligand for palladium-catalyzed asymmetric allylation

Co-reporter:Kohsuke Ohmatsu, Yoshiyuki Hara and Takashi Ooi

Chemical Science 2014 vol. 5(Issue 9) pp:3645-3650

Publication Date(Web):19 May 2014

DOI:10.1039/C4SC01032A

A method for the in situ generation of ion-paired chiral ligands from simple salts of ammonium phosphines and chiral Brønsted acids under phase-transfer conditions is established. The exploitation of this method in combinatorial ligand screening has enabled the rapid identification of the optimal ion-paired chiral ligand for the palladium-catalyzed asymmetric allylic alkylation of benzo[b]thiophen-2(3H)-ones.

Ligand-controlled E/Z selectivity and enantioselectivity in palladium-catalyzed allylation of benzofuranones with 1,2-disubstituted allylic carbonates

Co-reporter:Kohsuke Ohmatsu, Mitsunori Ito and Takashi Ooi

Chemical Communications 2014 vol. 50(Issue 35) pp:4554-4557

Publication Date(Web):23 Dec 2013

DOI:10.1039/C3CC49338E

The first highly E- and enantioselective allylic alkylation of prochiral carbon nucleophiles with 1,2-disubstituted allylic carbonates is reported. The key to the successful development of this protocol is the ability of modular ion-paired chiral ligands to simultaneously control the E/Z selectivity and enantioselectivity.

Enantioselective protonation of α-hetero carboxylic acid-derived ketene disilyl acetals under chiral ionic Brønsted acid catalysis

Co-reporter:Daisuke Uraguchi, Tomohito Kizu, Yuki Ohira and Takashi Ooi

Chemical Communications 2014 vol. 50(Issue 88) pp:13489-13491

Publication Date(Web):10 Sep 2014

DOI:10.1039/C4CC06081D

Highly enantioselective protonation of α-halo and alkoxy carboxylic acid-derived ketene disilyl acetals is achieved by using P-spiro chiral diaminodioxaphosphonium barfate as a Brønsted acid catalyst, where the enantiofacial discrimination by the catalyst mainly stems from the recognition of the electronic difference between two substituents on the ketene disilyl acetal.

Enantioselective formal α-allylation of nitroalkanes through a chiral iminophosphorane-catalyzed Michael reaction–Julia–Kocienski olefination sequence

Co-reporter:Daisuke Uraguchi, Shinji Nakamura, Hitoshi Sasaki, Yuki Konakade and Takashi Ooi

Chemical Communications 2014 vol. 50(Issue 26) pp:3491-3493

Publication Date(Web):06 Feb 2014

DOI:10.1039/C3CC49477B

A two-step sequence for the asymmetric formal α-allylation of nitroalkanes is disclosed. This new methodology relies on the development of a highly diastereo- and enantioselective conjugate addition of nitroalkanes to vinylic 2-phenyl-1H-tetrazol-5-ylsulfones using chiral triaminoiminophosphorane as a requisite base catalyst and subsequent Julia–Kocienski olefination under kinetic conditions.

Catalytic asymmetric Payne oxidation under the catalysis of P-spiro chiral triaminoiminophosphorane: application to the synthesis of N-sulfonyl oxaziridines

Co-reporter:Daisuke Uraguchi, Ryosuke Tsutsumi, Takashi Ooi

Tetrahedron 2014 70(8) pp: 1691-1701

Publication Date(Web):

DOI:10.1016/j.tet.2013.12.086

Catalytic Asymmetric Oxidation of N-Sulfonyl Imines with Hydrogen Peroxide–Trichloroacetonitrile System

Co-reporter:Daisuke Uraguchi ; Ryosuke Tsutsumi

Journal of the American Chemical Society 2013 Volume 135(Issue 22) pp:8161-8164

Publication Date(Web):May 16, 2013

DOI:10.1021/ja403491j

An efficient and highly enantioselective Payne-type oxidation of N-sulfonyl imines is developed. The reaction exhibits broad substrate generality and unique chemoselectivity based on the combined use of hydrogen peroxide and trichloroacetonitrile under the catalysis of P-spiro chiral triaminoiminophosphorane.

Asymmetric Substitution at the Tetrasubstituted Chiral Carbon: Catalytic Ring-Opening Alkylation of Racemic 2,2-Disubstituted Aziridines with 3-Substituted Oxindoles

Co-reporter:Kohsuke Ohmatsu ; Yuichiro Ando

Journal of the American Chemical Society 2013 Volume 135(Issue 50) pp:18706-18709

Publication Date(Web):December 4, 2013

DOI:10.1021/ja411647x

A highly diastereo- and enantioselective ring-opening alkylation of racemic 2,2-disubstituted aziridines with 3-substituted oxindoles is achieved under the catalysis of a chiral 1,2,3-triazolium salt. This reaction represents a hitherto unknown, catalytic stereoselective carbon–carbon bond formation through direct substitution at the tetrasubstituted chiral carbon.

Highly stereoselective Michael addition of azlactones to electron-deficient triple bonds under P-spiro chiral iminophosphorane catalysis: importance of protonation pathway

Co-reporter:Daisuke Uraguchi, Yusuke Ueki, Atsushi Sugiyama and Takashi Ooi

Chemical Science 2013 vol. 4(Issue 3) pp:1308-1311

Publication Date(Web):04 Jan 2013

DOI:10.1039/C2SC22027J

A catalyst-controlled, geometrically divergent asymmetric Michael addition of azlactones to methyl propiolate has been achieved under the catalysis of P-spiro chiral triaminoiminophosphoranes. An uncommon O-protonation of the intermediary allenic enolate is proposed to rationalize geometric control and its validity is proven by the development of highly Z- and enantioselective Michael addition of azlactones to cyanoacetylene with broad substrate scope.

Ionic Nucleophilic Catalysis of Chiral Ammonium Betaines for Highly Stereoselective Aldol Reaction from Oxindole-Derived Vinylic Carbonates

Co-reporter:Daisuke Uraguchi ; Kyohei Koshimoto

Journal of the American Chemical Society 2012 Volume 134(Issue 16) pp:6972-6975

Publication Date(Web):April 6, 2012

DOI:10.1021/ja3022939

A new strategy for developing stereoselective bond-forming reactions is introduced; it takes advantage of the ionic nucleophilic catalysis of chiral ammonium betaines to utilize vinylic esters simultaneously as the enolate precursor and the acylating agent for coupling with electrophiles. Its synthetic utility is clearly demonstrated by the realization of a highly diastereo- and enantioselective aldol reaction from oxindole-derived vinylic carbonates.

Highly Regio-, Diastereo-, and Enantioselective 1,6- and 1,8-Additions of Azlactones to Di- and Trienyl N-Acylpyrroles

Co-reporter:Daisuke Uraguchi ; Ken Yoshioka ; Yusuke Ueki

Journal of the American Chemical Society 2012 Volume 134(Issue 47) pp:19370-19373

Publication Date(Web):November 12, 2012

DOI:10.1021/ja310209g

A vinylog of Michael addition (1,6-addition) of azlactones to δ-substituted dienyl N-acylpyrroles has been developed with virtually complete 1,6-, diastereo-, and enantioselectivities by means of chiral P-spiro triaminoiminophosphorane as a catalyst. This system has been successfully extended to an unprecedented bis-vinylog of Michael addition (1,8-addition) of azlactones to ζ-substituted trienyl N-acylpyrroles with high levels of regio- and stereocontrol.

Exploiting the Modularity of Ion-Paired Chiral Ligands for Palladium-Catalyzed Enantioselective Allylation of Benzofuran-2(3H)-ones

Co-reporter:Kohsuke Ohmatsu ; Mitsunori Ito ; Tomoatsu Kunieda

Journal of the American Chemical Society 2012 Volume 135(Issue 2) pp:590-593

Publication Date(Web):December 27, 2012

DOI:10.1021/ja312125a

A highly enantioselective allylation of benzofuran-2(3H)-ones is achieved under Pd catalysis by taking full advantage of the structural modularity of ion-paired chiral ligands.

Highly stereoselective catalytic conjugate addition of acyl anion equivalent to nitroolefins

Co-reporter:Daisuke Uraguchi, Yusuke Ueki and Takashi Ooi

Chemical Science 2012 vol. 3(Issue 3) pp:842-845

Publication Date(Web):15 Nov 2011

DOI:10.1039/C1SC00678A

Highly enantioselective conjugate addition of 2-unsubstituted azlactone 3 to various nitroolefins 4 was accomplished by the selective utilization of supramolecularly assembled, chiral tetraaminophosphonium aryloxide–arylhydroxide 1a·[2a]2 as a requisite catalyst. The key to this achievement is the polarity dependence of the molecular associations of type 1·[2]n and the crucial role of the proximal arylhydroxide 2 as a proton donor. The present method offers an attractive route to various optically active amino carbonyl compounds including β2-amino acids.

Chiral ionic Brønsted acid–achiral Brønsted base synergistic catalysis for asymmetric sulfa-Michael addition to nitroolefins

Co-reporter:Daisuke Uraguchi, Natsuko Kinoshita, Daisuke Nakashima and Takashi Ooi

Chemical Science 2012 vol. 3(Issue 11) pp:3161-3164

Publication Date(Web):06 Jul 2012

DOI:10.1039/C2SC20698F

A highly enantioselective sulfa-Michael addition to aromatic and aliphatic nitroolefins is achieved under the synergistic catalysis of chiral, ionic Brønsted acid homo-1b·HBArF and 2,6-lutidine. The potential utility of this new method is clearly demonstrated by its application to the syntheses of a novel, optically active taurine derivative and β-sultam.

Catalytic asymmetric Mannich-type reactions of α-cyano α-sulfonyl carbanions

Co-reporter:Kohsuke Ohmatsu, Ayano Goto and Takashi Ooi

Chemical Communications 2012 vol. 48(Issue 64) pp:7913-7915

Publication Date(Web):16 May 2012

DOI:10.1039/C2CC32398B

An efficient asymmetric Mannich-type reaction of α-cyano α-sulfonyl carbanions has been achieved by exploiting the structural modularity and anion-recognition ability of chiral 1,2,3-triazolium ions. This protocol has proven to be applicable to a variety of N-Boc imines and cyanosulfones, affording β-amino α-cyanosulfones in excellent yields with high stereoselectivities.

Nitroolefins as a Nucleophilic Component for Highly Stereoselective Aza Henry Reaction under the Catalysis of Chiral Ammonium Betaines

Co-reporter:Dr. Daisuke Uraguchi;Keigo Oyaizu ;Dr. Takashi Ooi

Chemistry - A European Journal 2012 Volume 18( Issue 27) pp:8306-8309

Publication Date(Web):

DOI:10.1002/chem.201201259

Base-Catalyzed Direct Aldolization of -Alkyl--Hydroxy Trialkyl Phosphonoacetates

Co-reporter:Michael T. Corbett;Dr. Daisuke Uraguchi;Dr. Takashi Ooi;Dr. Jeffrey S. Johnson

Angewandte Chemie International Edition 2012 Volume 51( Issue 19) pp:4685-4689

Publication Date(Web):

DOI:10.1002/anie.201200559

Base-Catalyzed Direct Aldolization of -Alkyl--Hydroxy Trialkyl Phosphonoacetates

Co-reporter:Michael T. Corbett;Dr. Daisuke Uraguchi;Dr. Takashi Ooi;Dr. Jeffrey S. Johnson

Angewandte Chemie 2012 Volume 124( Issue 19) pp:4763-4767

Publication Date(Web):

DOI:10.1002/ange.201200559

Chiral 1,2,3-Triazoliums as New Cationic Organic Catalysts with Anion-Recognition Ability: Application to Asymmetric Alkylation of Oxindoles

Co-reporter:Kohsuke Ohmatsu ; Mari Kiyokawa

Journal of the American Chemical Society 2011 Volume 133(Issue 5) pp:1307-1309

Publication Date(Web):January 4, 2011

DOI:10.1021/ja1102844

Chiral 1,2,3-triazoliums have been designed, and the rational structural modification based on their unique anion-binding abilities has led to the establishment of the highly enantioselective alkylation of 3-substituted oxindoles.

Controlled Assembly of Chiral Tetraaminophosphonium AryloxideArylhydroxide(s) in Solution

Co-reporter:Dr. Daisuke Uraguchi;Yusuke Ueki ;Dr. Takashi Ooi

Angewandte Chemie International Edition 2011 Volume 50( Issue 16) pp:3681-3683

Publication Date(Web):

DOI:10.1002/anie.201007752

Controlled Assembly of Chiral Tetraaminophosphonium AryloxideArylhydroxide(s) in Solution

Co-reporter:Dr. Daisuke Uraguchi;Yusuke Ueki ;Dr. Takashi Ooi

Angewandte Chemie 2011 Volume 123( Issue 16) pp:3765-3767

Publication Date(Web):

DOI:10.1002/ange.201007752

Catalytic Asymmetric Protonation of α-Amino Acid-Derived Ketene Disilyl Acetals Using P-Spiro Diaminodioxaphosphonium Barfates as Chiral Proton

Co-reporter:Daisuke Uraguchi ; Natsuko Kinoshita

Journal of the American Chemical Society 2010 Volume 132(Issue 35) pp:12240-12242

Publication Date(Web):August 17, 2010

DOI:10.1021/ja105945z

Chiral diaminodioxaphosphonium salts have been developed and their unique abilities as a chiral proton have been revealed through the establishment of a highly enantioselective protonation of α-amino acid-derived ketene disilyl acetals.

Catalytic asymmetric hydrophosphonylation of ynones

Co-reporter:Daisuke Uraguchi, Takaki Ito, Shinji Nakamura and Takashi Ooi

Chemical Science 2010 vol. 1(Issue 4) pp:488-490

Publication Date(Web):24 Jun 2010

DOI:10.1039/C0SC00268B

Catalytic, highly enantioselective hydrophosphonylation of ynones has been achieved by exploiting the characteristic features of in situ generated chiral tetraaminophosphonium phosphite.

Flexible synthesis, structural determination, and synthetic application of a new C1-symmetric chiral ammonium betaine

Co-reporter:Daisuke Uraguchi, Kyohei Koshimoto and Takashi Ooi

Chemical Communications 2010 vol. 46(Issue 2) pp:300-302

Publication Date(Web):25 Nov 2009

DOI:10.1039/B916627K

A C1-symmetric chiral ammonium betaine has been developed, and its intramolecular ion-pairing structure in solid state and its catalytic performance to achieve the highly stereoselective Mannich-type reaction of 2-alkoxythiazol-5(4H)-ones are revealed.

Chiral Ammonium Betaines as Ionic Nucleophilic Catalysts

Co-reporter:Daisuke Uraguchi Dr.;Kyohei Koshimoto;Shuhei Miyake Dr.

Angewandte Chemie 2010 Volume 122( Issue 32) pp:5699-5701

Publication Date(Web):

DOI:10.1002/ange.201002315

Performance of C1-symmetric chiral ammonium betaines as catalysts for the enantioselective Mannich-type reaction of α-nitrocarboxylates

Co-reporter:Daisuke Uraguchi, Kyohei Koshimoto, Chisato Sanada, Takashi Ooi

Tetrahedron: Asymmetry 2010 Volume 21(9–10) pp:1189-1190

Publication Date(Web):17 May 2010

DOI:10.1016/j.tetasy.2010.04.006

The catalytic performance of C1-symmetric chiral ammonium betaines in the enantioselective direct Mannich-type reaction of α-nitrocarboxylates with N-Boc imines has been investigated. The most effective catalyst structure has been identified; this provides a reliable synthetic route to a variety of enantiomerically enriched α-tetrasubstituted α,β-diamino acid derivatives.

Chiral Ammonium Betaines as Ionic Nucleophilic Catalysts

Co-reporter:Daisuke Uraguchi Dr.;Kyohei Koshimoto;Shuhei Miyake Dr.

Angewandte Chemie International Edition 2010 Volume 49( Issue 32) pp:5567-5569

Publication Date(Web):

DOI:10.1002/anie.201002315

Catalytic Asymmetric Direct Henry Reaction of Ynals: Short Syntheses of (2S,3R)-(+)-XestoaminolC and ()-Codonopsinines

Co-reporter:Dr. Daisuke Uraguchi;Shinji Nakamura ;Dr. Takashi Ooi

Angewandte Chemie 2010 Volume 122( Issue 41) pp:7724-7727

Publication Date(Web):

DOI:10.1002/ange.201004072

Catalytic Asymmetric Direct Henry Reaction of Ynals: Short Syntheses of (2S,3R)-(+)-XestoaminolC and ()-Codonopsinines

Co-reporter:Dr. Daisuke Uraguchi;Shinji Nakamura ;Dr. Takashi Ooi

Angewandte Chemie International Edition 2010 Volume 49( Issue 41) pp:7562-7565

Publication Date(Web):

DOI:10.1002/anie.201004072

Chiral Arylaminophosphonium Barfates as a New Class of Charged Brønsted Acid for the Enantioselective Activation of Nonionic Lewis Bases

Co-reporter:Daisuke Uraguchi ; Daisuke Nakashima

Journal of the American Chemical Society 2009 Volume 131(Issue 21) pp:7242-7243

Publication Date(Web):May 11, 2009

DOI:10.1021/ja903271t

Heterochiral [7.7]-P-spirocyclic arylaminophosphonium barfates have been designed as a novel charged, cationic Brønsted acid catalyst, and their catalytic and stereocontrolling abilities have been clearly demonstrated in the development of the unprecedented, highly enantioselective conjugate addition of arylamines to nitroolefins. This study uncovers a new function of chiral tetraaminophosphonium cations and its potential synthetic utility, thereby providing a new avenue to the molecular design of chiral charged Brønsted acid catalysts and their applications.

Al Lewis acid-catalyzed regiodivergent 1,2-rearrangement of α-siloxy aldehydes: scope and mechanism

Co-reporter:Kohsuke Ohmatsu, Takayuki Tanaka, Takashi Ooi, Keiji Maruoka

Tetrahedron 2009 65(36) pp: 7516-7522

Publication Date(Web):

DOI:10.1016/j.tet.2009.06.126

Inside Cover: Site-Directed Asymmetric Quaternization of a Peptide Backbone at a C-Terminal Azlactone (Angew. Chem. Int. Ed. 4/2009)

Co-reporter:Daisuke Uraguchi Dr.;Yoshihiro Asai Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 4) pp:

Publication Date(Web):

DOI:10.1002/anie.200990001

Co-reporter:Daisuke Uraguchi;Yusuke Ueki

Science 2009 Volume 326(Issue 5949) pp:

Publication Date(Web):

DOI:10.1126/science.1176758

Catalytic Assembly

Most asymmetric catalysts employed in organic chemistry are assembled through binding of chiral ligands to one or more metal ions. Uraguchi et al. (p. 120, published online 27 August) show that a highly selective catalyst can assemble through hydrogen bonding from a small collection of small molecules in the absence of metals. In the solid state, the catalyst comprises a central chiral phosphonium cation bound to two phenol molecules, which in turn bind a charge-compensating phenoxide ion. In solution, an oxazolone derivative appears to be able to bind in place of the phenoxide, spurring its stereoselective addition to a broad range of esters.

Site-Directed Asymmetric Quaternization of a Peptide Backbone at a C-Terminal Azlactone

Co-reporter:Daisuke Uraguchi Dr.;Yoshihiro Asai Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 4) pp:733-737

Publication Date(Web):

DOI:10.1002/anie.200803661

Site-Directed Asymmetric Quaternization of a Peptide Backbone at a C-Terminal Azlactone

Co-reporter:Daisuke Uraguchi Dr.;Yoshihiro Asai Dr.

Angewandte Chemie 2009 Volume 121( Issue 4) pp:747-751

Publication Date(Web):

DOI:10.1002/ange.200803661

Innentitelbild: Site-Directed Asymmetric Quaternization of a Peptide Backbone at a C-Terminal Azlactone (Angew. Chem. 4/2009)

Co-reporter:Daisuke Uraguchi Dr.;Yoshihiro Asai Dr.

Angewandte Chemie 2009 Volume 121( Issue 4) pp:

Publication Date(Web):

DOI:10.1002/ange.200990001

Catalytic Asymmetric Ring Openings of Meso and Terminal Aziridines with Halides Mediated by Chiral 1,2,3-Triazolium Silicates

Co-reporter:Kohsuke Ohmatsu ; Yuta Hamajima

Journal of the American Chemical Society () pp:

Publication Date(Web):May 14, 2012

DOI:10.1021/ja3028668

Catalytic asymmetric chloride and bromide ring openings of meso aziridines with trimethylsilyl halides have been developed using modular chiral 1,2,3-triazolium chlorides as catalysts. Control experiments suggest the reaction pathway involving hypervalent silicate ions as reactive intermediates. The application of this system to the efficient kinetic resolution of terminal aziridines is also reported.

Unique site-selectivity control in asymmetric Michael addition of azlactone to alkenyl dienyl ketones enabled by P-spiro chiral iminophosphorane catalysis

Co-reporter:Ken Yoshioka, Kohei Yamada, Daisuke Uraguchi and Takashi Ooi

Chemical Communications 2017 - vol. 53(Issue 40) pp:NaN5498-5498

Publication Date(Web):2017/04/20

DOI:10.1039/C7CC01715D

Vinylogy in nitronates: utilization of α-aryl conjugated nitroolefins as a nucleophile for a highly stereoselective aza-Henry reaction

Co-reporter:Keigo Oyaizu, Daisuke Uraguchi and Takashi Ooi

Chemical Communications 2015 - vol. 51(Issue 21) pp:NaN4439-4439

Publication Date(Web):2015/02/03

DOI:10.1039/C4CC10261D

Flexible synthesis, structural determination, and synthetic application of a new C1-symmetric chiral ammonium betaine

Co-reporter:Daisuke Uraguchi, Kyohei Koshimoto and Takashi Ooi

Chemical Communications 2010 - vol. 46(Issue 2) pp:NaN302-302

Publication Date(Web):2009/11/25

DOI:10.1039/B916627K

Ligand-controlled E/Z selectivity and enantioselectivity in palladium-catalyzed allylation of benzofuranones with 1,2-disubstituted allylic carbonates

Co-reporter:Kohsuke Ohmatsu, Mitsunori Ito and Takashi Ooi

Chemical Communications 2014 - vol. 50(Issue 35) pp:NaN4557-4557

Publication Date(Web):2013/12/23

DOI:10.1039/C3CC49338E

Catalytic asymmetric Mannich-type reactions of α-cyano α-sulfonyl carbanions

Co-reporter:Kohsuke Ohmatsu, Ayano Goto and Takashi Ooi

Chemical Communications 2012 - vol. 48(Issue 64) pp:NaN7915-7915

Publication Date(Web):2012/05/16

DOI:10.1039/C2CC32398B

Highly stereoselective Michael addition of azlactones to electron-deficient triple bonds under P-spiro chiral iminophosphorane catalysis: importance of protonation pathway

Co-reporter:Daisuke Uraguchi, Yusuke Ueki, Atsushi Sugiyama and Takashi Ooi

Chemical Science (2010-Present) 2013 - vol. 4(Issue 3) pp:NaN1311-1311

Publication Date(Web):2013/01/04

DOI:10.1039/C2SC22027J

Catalytic asymmetric hydrophosphonylation of ynones

Co-reporter:Daisuke Uraguchi, Takaki Ito, Shinji Nakamura and Takashi Ooi

Chemical Science (2010-Present) 2010 - vol. 1(Issue 4) pp:NaN490-490

Publication Date(Web):2010/06/24

DOI:10.1039/C0SC00268B

Catalytic, highly enantioselective hydrophosphonylation of ynones has been achieved by exploiting the characteristic features of in situ generated chiral tetraaminophosphonium phosphite.

In situ generation of ion-paired chiral ligands: rapid identification of the optimal ligand for palladium-catalyzed asymmetric allylation

Co-reporter:Kohsuke Ohmatsu, Yoshiyuki Hara and Takashi Ooi

Chemical Science (2010-Present) 2014 - vol. 5(Issue 9) pp:NaN3650-3650

Publication Date(Web):2014/05/19

DOI:10.1039/C4SC01032A

Enantioselective reductive multicomponent coupling reactions between isatins and aldehydes

Co-reporter:Matthew A. Horwitz, Naoya Tanaka, Takuya Yokosaka, Daisuke Uraguchi, Jeffrey S. Johnson and Takashi Ooi

Chemical Science (2010-Present) 2015 - vol. 6(Issue 11) pp:NaN6090-6090

Publication Date(Web):2015/07/30

DOI:10.1039/C5SC02170G

Highly stereoselective catalytic conjugate addition of acyl anion equivalent to nitroolefins

Co-reporter:Daisuke Uraguchi, Yusuke Ueki and Takashi Ooi