Koji Hirano

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Organization: Osaka University

Department: Department of Applied Chemistry, Faculty of Engineering

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Organic Chemistry

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A Divergent Approach to Indoles and Oxazoles from Enamides by Directing-Group-Controlled Cu-Catalyzed Intramolecular C–H Amination and Alkoxylation

Co-reporter:Chiaki Yamamoto, Kazutaka Takamatsu, Koji Hirano, and Masahiro Miura

The Journal of Organic Chemistry September 1, 2017 Volume 82(Issue 17) pp:9112-9112

Publication Date(Web):August 7, 2017

DOI:10.1021/acs.joc.7b01667

A directing-group-controlled, copper-catalyzed divergent approach to indoles and oxazoles from enamides has been developed. The picolinamide-derived enamides undergo the intramolecular aromatic C–H amination in the presence of a Cu(OPiv)2 catalyst and an MnO2 oxidant to form the corresponding indoles in good yields. On the other hand, simpler aryl- or alkyl-substituted enamides are converted to the 2,4,5-trisubstituted oxazole frameworks via vinylic C–H alkoxylation under identical conditions. The copper catalysis can provide uniquely divergent access to indole and oxazole heteroaromatic cores of great importance in medicinal and material chemistry.

Copper/Bisphosphine Catalysts in the Internally Borylative Aminoboration of Unactivated Terminal Alkenes with Bis(pinacolato)diboron

Co-reporter:Kodai Kato, Koji Hirano, and Masahiro Miura

The Journal of Organic Chemistry October 6, 2017 Volume 82(Issue 19) pp:10418-10418

Publication Date(Web):August 29, 2017

DOI:10.1021/acs.joc.7b01874

Cu(I)/modified dppbz catalyst systems for the regioselective aminoboration of unactivated terminal alkenes have been developed. The bisphosphine-based Cu catalysis enables the introduction of the readily transformable Bpin group at the more congested internal position and shows better regioselectivity for broader terminal alkenes involving sterically demanding allylbenzenes, which are relatively challenging substrates in the previous IPrCuBr catalysis. Additionally, the second-generation catalyst systems accommodate the exo-methylene-type disubstituted alkenes to deliver the corresponding aminoborated products in good yields with a high regioselectivity.

Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles

Co-reporter:Atifah Najib, Koji Hirano, and Masahiro Miura

Organic Letters May 5, 2017 Volume 19(Issue 9) pp:

Publication Date(Web):April 27, 2017

DOI:10.1021/acs.orglett.7b01022

A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution of secondary benzyl carbonates with amides and amines proceeds to form the corresponding optically active benzylamines in good yields with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner. Additionally, the asymmetric Pd catalysis can also be applicable to phenol nucleophiles, thus delivering chiral ethers with acceptable yields and enantioselectivity.

Metal-Free Electrophilic Phosphination/Cyclization of Alkynes

Co-reporter:Yuto Unoh, Koji Hirano, and Masahiro Miura

Journal of the American Chemical Society May 3, 2017 Volume 139(Issue 17) pp:6106-6106

Publication Date(Web):April 17, 2017

DOI:10.1021/jacs.7b02977

A metal-free electrophilic phosphination reaction has been developed. Electrophilic phosphorus species generated in situ from secondary phosphine oxides and Tf2O smoothly couple with alkynes possessing pendant nucleophiles to afford the corresponding phosphinated cyclization products in good yield. Preliminary NMR studies show that phosphirenium species may be involved as intermediates of the cyclization reactions.

Nickel-Catalyzed Directed C6-Selective C–H Alkylation of 2-Pyridones with Dienes and Activated Alkenes

Co-reporter:Wataru Miura, Koji Hirano, and Masahiro Miura

The Journal of Organic Chemistry May 19, 2017 Volume 82(Issue 10) pp:5337-5337

Publication Date(Web):April 27, 2017

DOI:10.1021/acs.joc.7b00682

A pyridine-directed, C6-selective nickel-catalyzed ring-contracting C–H alkylation of 2-pyridones with 1,5-cyclooctadiene (cod) has been developed. The reaction proceeds smoothly under external-ligand-free conditions and is accelerated uniquely by a K3PO4 base. Preliminary mechanistic investigations with deuterium-labeled substrates and related reactions with some alkenes are also disclosed.

Recent advances in diphosphination of alkynes and alkenes

Co-reporter:Koji Hirano, Masahiro Miura

Tetrahedron Letters 2017 Volume 58, Issue 46(Issue 46) pp:

Publication Date(Web):15 November 2017

DOI:10.1016/j.tetlet.2017.10.018

•This digest highlights recent advances in diphosphination of alkynes and alkenes.•The reported approaches are categorized into several types of reactions.•The scope, limitation and mechanism of the reactions are briefly summarized.1,2-Bis(diphenylphosphino)ethenes and -ethanes (DPPEs) are among representative supporting ligands in transition metal catalysts, which can promote otherwise challenging organic transformations with high efficiency and selectivity. Such bidentately coordinating ligands are conventionally prepared by nucleophilic substitution reactions of halogenated carbon electrophiles with nucleophilic metal phosphides. However, they suffer from poor functional group compatibility and/or tedious preparation of highly functionalized starting substrates. In this context, additions of phosphines to readily available and simple alkynes and alkenes have recently received significant attention. This digest paper focuses on recent developments of diphosphination of alkynes and alkenes for the synthesis of DPPE-type ligands. The reported approaches are categorized into several types of reactions, and their scope, limitation, and mechanism are briefly summarized.Download high-res image (56KB)Download full-size image

Copper-Mediated Decarboxylative Coupling of Benzamides with ortho-Nitrobenzoic Acids by Directed C−H Cleavage

Co-reporter:Kazutaka Takamatsu; Dr. Koji Hirano; Dr. Masahiro Miura

Angewandte Chemie International Edition 2017 Volume 56(Issue 19) pp:5353-5357

Publication Date(Web):2017/05/02

DOI:10.1002/anie.201701918

AbstractA copper-mediated decarboxylative coupling of benzamides with ortho-nitrobenzoic acids by 8-aminoquinoline-directed C−H cleavage has been developed. This reaction proceeds smoothly with only a copper salt to produce the corresponding biaryl compounds in good yields. The products can be easily transformed into various nitrogen-containing heterocyclic compounds. Moreover, the combination of copper and a suitable base promotes a decarboxylative C−H arylation and cyclization sequence to deliver phenanthridinone derivatives in one pot.

Copper-Catalyzed Regio- and Stereoselective Aminoboration of Alkenylboronates

Co-reporter:Daiki Nishikawa, Koji Hirano, and Masahiro Miura

Organic Letters 2016 Volume 18(Issue 19) pp:4856-4859

Publication Date(Web):September 20, 2016

DOI:10.1021/acs.orglett.6b02338

A copper-catalyzed aminoboration of alkenyl dan boronates (dan = 1,8-diaminonaphthyl) with diboron reagents and hydroxylamines has been developed. The reaction proceeds regio- and stereoselectively to form the corresponding β-boryl-α-aminoboronic acid derivatives of potent interest in medicinal chemistry. Additionally, the ligand-controlled syn/anti diastereoselectivity switching and preliminary asymmetric catalysis are also described.

Rhodium-Catalyzed C6-Selective C–H Borylation of 2-Pyridones

Co-reporter:Wataru Miura, Koji Hirano, and Masahiro Miura

Organic Letters 2016 Volume 18(Issue 15) pp:3742-3745

Publication Date(Web):July 15, 2016

DOI:10.1021/acs.orglett.6b01762

A pyridine-directed, rhodium-catalyzed C6-selective C–H borylation of 2-pyridones with bis(pinacolato)diboron (pinB–Bpin) has been developed. The reaction proceeds smoothly under relatively mild conditions, and the corresponding C6-borylated 2-pyridones are obtained with perfect site selectivity. Subsequent palladium-catalyzed Suzuki–Miyaura cross-coupling is followed by the removal of the pyridine directing group to form the C6-arylated NH-pyridone in an acceptable overall yield.

Palladium-Catalyzed Asymmetric Benzylic Alkylation of Active Methylene Compounds with -Naphthylbenzyl Carbonates and Pivalates

Co-reporter:Sho Tabuchi;Dr. Koji Hirano;Dr. Masahiro Miura

Angewandte Chemie 2016 Volume 128( Issue 24) pp:7087-7091

Publication Date(Web):

DOI:10.1002/ange.201602075

Abstract

A Pd/(R)-H₈-BINAP-catalyzed asymmetric benzylic alkylation of active methylene compounds has been developed. The reaction proceeds without the use of an external base, and the starting racemic diarylmethyl carbonates are converted into the optically active coupling products which contain the benzylic chiral stereocenter by a dynamic kinetic asymmetric transformation (DYKAT). Additionally, with suitable carbonates bases, the same palladium catalysis allows the corresponding pivalates to be adopted in the same DYKAT process.

Palladium-Catalyzed Asymmetric Benzylic Alkylation of Active Methylene Compounds with -Naphthylbenzyl Carbonates and Pivalates

Co-reporter:Sho Tabuchi;Dr. Koji Hirano;Dr. Masahiro Miura

Angewandte Chemie International Edition 2016 Volume 55( Issue 24) pp:6973-6977

Publication Date(Web):

DOI:10.1002/anie.201602075

Abstract

Copper-Catalyzed Intramolecular Benzylic C–H Amination for the Synthesis of Isoindolinones

Co-reporter:Chiaki Yamamoto, Kazutaka Takamatsu, Koji Hirano, and Masahiro Miura

The Journal of Organic Chemistry 2016 Volume 81(Issue 17) pp:7675-7684

Publication Date(Web):August 9, 2016

DOI:10.1021/acs.joc.6b01393

A copper-catalyzed intramolecular amination occurs at the benzylic C–H of 2-methylbenzamides to deliver the corresponding isoindolinones of great interest in medicinal chemistry. The mild and abundant MnO2 works well as a terminal oxidant, and the reaction proceeds smoothly under potentially explosive organic peroxide-free conditions. Additionally, the directing-group-dependent divergent mechanisms are proposed: 8-aminoquinoline-containing benzamides include a Cu-mediated organometallic pathway whereas an aminyl radical-promoted Hofmann–Loffler–Freytag (HLF)-type mechanism can be operative in the case of N-naphthyl-substituted substrates.

Copper-Catalyzed Regioselective Ring-Opening Hydroamination of Methylenecyclopropanes

Co-reporter:Daiki Nishikawa, Ryosuke Sakae, Yuya Miki, Koji Hirano, and Masahiro Miura

The Journal of Organic Chemistry 2016 Volume 81(Issue 24) pp:12128-12134

Publication Date(Web):December 2, 2016

DOI:10.1021/acs.joc.6b02483

A copper-catalyzed ring-opening hydroamination of methylenecyclopropanes with polymethylhydrosiloxane and O-benzoylhydroxylamines has been developed. The cyclopropane C–C bond cleavage occurs selectively at the more congested proximal position, and the corresponding homoallylamines are obtained in good to excellent yields. The umpolung electrophilic amination strategy with the hydroxylamine derivatives can provide a new reaction mode of methylenecyclopropanes in the catalytic hydroamination reaction.

Asymmetric Synthesis of α-Aminoboronic Acid Derivatives by Copper-Catalyzed Enantioselective Hydroamination

Co-reporter:Daiki Nishikawa; Koji Hirano;Masahiro Miura

Journal of the American Chemical Society 2015 Volume 137(Issue 50) pp:15620-15623

Publication Date(Web):December 10, 2015

DOI:10.1021/jacs.5b09773

A copper-catalyzed regio- and enantioselective hydroamination of alkenyl dan boronates (dan =1,8-diaminonaphthyl) with hydrosilanes and hydroxylamines proceeds to deliver the chiral α-aminoboronic acids in good yields with high enantiomeric ratios. The key to success is the introduction of an umpolung, electrophilic amination strategy. The copper catalysis can provide an unprecedented catalytic asymmetric approach to alkyl-substituted chiral α-aminoboronic acid derivatives of great potential in the fields of organic synthesis and medicinal chemistry.

Ligand-Controlled Regiodivergent Cu-Catalyzed Aminoboration of Unactivated Terminal Alkenes

Co-reporter:Ryosuke Sakae; Koji Hirano;Masahiro Miura

Journal of the American Chemical Society 2015 Volume 137(Issue 20) pp:6460-6463

Publication Date(Web):May 7, 2015

DOI:10.1021/jacs.5b02775

A ligand-controlled regiodivergent Cu-catalyzed aminoboration of unactivated terminal alkenes with diboron reagents and hydroxylamines has been developed. The xantphos-ligated CuCl complex guides the boron and amino groups to the terminal and internal positions, respectively. On the other hand, the opposite regioisomers are selectively obtained under the N-heterocyclic carbene-based IPrCuBr catalysis. The two Cu catalysts can readily transform simple and abundant terminal alkenes into highly valuable β-borylalkylamines regiodivergently.

Copper-Catalyzed Formal [4 + 1] Cycloaddition of Benzamides and Isonitriles via Directed C–H Cleavage

Co-reporter:Kazutaka Takamatsu, Koji Hirano, and Masahiro Miura

Organic Letters 2015 Volume 17(Issue 16) pp:4066-4069

Publication Date(Web):August 3, 2015

DOI:10.1021/acs.orglett.5b01986

A copper-catalyzed formal [4 + 1] cycloaddition of benzamides and isonitriles via 8-aminoquinoline-directed C–H cleavage has been developed. The reaction proceeds well even in the presence of a base metal catalyst, CuBr·SMe2, alone to deliver the corresponding 3-iminoisoindolinones in good yields. Moreover, the unique acceleration effects of diphenyl sulfide are also disclosed.

Copper-Catalyzed Stereoselective Aminoboration of Bicyclic Alkenes

Co-reporter:Ryosuke Sakae;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2015 Volume 54( Issue 2) pp:613-617

Publication Date(Web):

DOI:10.1002/anie.201409104

Abstract

A copper-catalyzed aminoboration of bicyclic alkenes, including oxa- and azabenzonorbornadienes, has been developed. With this method, amine and boron moieties are simultaneously introduced at an olefin with exo selectivity. Subsequent stereospecific transformations of the boryl group can provide oxygen- and nitrogen-rich cyclic molecules with motifs that may be found in natural products or pharmaceutically active compounds. Moreover, a catalytic asymmetric variant of this transformation was realized by using a copper complex with a chiral bisphosphine ligand, namely (R,R)-Ph-BPE.

Copper-Mediated Formally Dehydrative Biaryl Coupling of Azine N-Oxides and Oxazoles

Co-reporter:Riko Odani, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2015 Volume 80(Issue 4) pp:2384-2391

Publication Date(Web):January 22, 2015

DOI:10.1021/acs.joc.5b00037

A copper-mediated formally dehydrative biaryl coupling of azine N-oxides and oxazoles has been developed. The C–C bond-forming process proceeds, accompanied by the removal of the oxygen atom from the azine core, to directly afford the azine–oxazole biaryl linkage. Moreover, this system requires no noble transition metals such as palladium and rhodium, which are common promotors in the related dehydrogenative couplings with the azine N-oxide. Thus, the present protocol can provide a unique and less expensive approach to the azine-containing biheteroaryls of substantial interest in pharmaceutical and medicinal chemistry.

Synthesis of Indolines by Copper-Mediated Intramolecular Aromatic C–H Amination

Co-reporter:Kazutaka Takamatsu, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2015 Volume 80(Issue 6) pp:3242-3249

Publication Date(Web):February 26, 2015

DOI:10.1021/acs.joc.5b00307

A Cu(OAc)2-mediated intramolecular aromatic C–H amination proceeds with the aid of a picolinamide-type bidentate coordination group to deliver the corresponding indolines in good yields. The reaction occurs smoothly even under noble-metal-free conditions, and in some cases the use of an MnO2 terminal oxidant renders the process catalytic in Cu. The mild oxidation aptitude of Cu(OAc)2 and/or MnO2 accommodates the formation of electron-rich thiophene- and indole-fused indoline analogues. The Cu-based system can provide an effective approach to various indolines of potent interest in pharmaceutical and medicinal chemistry.

Stereospecific Pd-Catalyzed Intermolecular C(sp3)C(sp) Cross-Coupling of Diarylmethyl Carbonates and Terminal Alkynes Under Base-Free Conditions

Co-reporter:Sho Tabuchi;Dr. Koji Hirano;Dr. Masahiro Miura

Chemistry - A European Journal 2015 Volume 21( Issue 47) pp:16823-16827

Publication Date(Web):

DOI:10.1002/chem.201503647

Abstract

A palladium-catalyzed intermolecular decarboxylative C(sp³)–C(sp) coupling of diarylmethyl carbonates and terminal alkynes has been developed. The reaction proceeds smoothly under external base-free conditions to deliver the corresponding alkynylated diarylmethanes with the liberation of CO₂ and MeOH as the sole byproducts. Moreover, enantioenriched diarylmethyl carbonates are stereospecifically converted to optically active cross-coupling products with inversion of configuration. Thus, the stereospecific palladium catalysis can provide new and unique access to the alkynylated chiral tertiary stereocenters, which are relatively difficult to construct by conventional methods.

Copper-Catalyzed Stereoselective Aminoboration of Bicyclic Alkenes

Co-reporter:Ryosuke Sakae;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2015 Volume 127( Issue 2) pp:623-627

Publication Date(Web):

DOI:10.1002/ange.201409104

Abstract

Synthesis of Carbazoles by Copper-Catalyzed Intramolecular C–H/N–H Coupling

Co-reporter:Kazutaka Takamatsu, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2014 Volume 16(Issue 11) pp:2892-2895

Publication Date(Web):May 9, 2014

DOI:10.1021/ol501037j

A Cu-catalyzed intramolecular C–H amination for the synthesis of carbazoles has been developed. The key to success is the installation of the picolinamide-based directing group, which is spontaneously removed after the coupling event. The Cu catalysis proceeded smoothly under Pd- and I(III)-free conditions, and its mild oxidation aptitude enables the rapid and concise construction of heteroatom-incorporated carbazole core π-systems.

Copper-Catalyzed Enantioselective Formal Hydroamination of Oxa- and Azabicyclic Alkenes with Hydrosilanes and Hydroxylamines

Co-reporter:Yuya Miki, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2014 Volume 16(Issue 5) pp:1498-1501

Publication Date(Web):February 20, 2014

DOI:10.1021/ol5003219

A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addition of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbornanylamines in good yields and good enantiomeric ratios.

Highly Stereoselective Synthesis of (Borylmethyl)cyclopropylamines by Copper-Catalyzed Aminoboration of Methylenecyclopropanes

Co-reporter:Ryosuke Sakae, Naoki Matsuda, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2014 Volume 16(Issue 4) pp:1228-1231

Publication Date(Web):February 3, 2014

DOI:10.1021/ol5001507

A Cu-catalyzed aminoboration of 1-methylenecyclopropanes with bis(pinacolato)diboron and O-benzoyl-N,N-dialkylhydroxylamines has been developed. The Cu catalysis provides a rapid and concise access to (borylmethyl)cyclopropylamines in a highly regio- and diastereoselective manner. The products obtained can be useful building blocks for the synthesis of potential antidepressants, trans-2-arylcyclopropylamine derivatives.

Manganese-Mediated C3-Selective Direct Alkylation and Arylation of 2-Pyridones with Diethyl Malonates and Arylboronic Acids

Co-reporter:Akihiro Nakatani, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2014 Volume 79(Issue 3) pp:1377-1385

Publication Date(Web):January 23, 2014

DOI:10.1021/jo4027885

A manganese-mediated dehydrogenative direct alkylation of 2-pyridones with diethyl malonates has been developed. A similar reaction system is applicable to the direct arylation with arylboronic acids. These manganese-based reactions occur regioselectively at the C3 position of the 2-pyridones. The observed high C3 regioselectivity can complement precedented C–H functionalization protocols of the 2-pyridones in view of the site selectivity.

Synthesis of Triarylmethanes by Palladium-Catalyzed C–H/C–O Coupling of Oxazoles and Diarylmethanol Derivatives

Co-reporter:Sho Tabuchi, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2014 Volume 79(Issue 12) pp:5401-5411

Publication Date(Web):June 9, 2014

DOI:10.1021/jo5010636

A PdCl2(MeCN)2/PPhCy2 catalyst couples oxazoles with diarylmethyl carbonates or pivalates to form the corresponding triarylmethanes in good yields. The catalysis involves successive secondary benzylic sp3 C–O and heteroaromatic sp2 C–H cleavages and provides an effective access to heteroarene-containing triarylmethanes from nonhalogenated and nonmetalated starting materials, which is complementary to precedented cross-coupling technologies with organic halides and organometallic reagents.

Copper-Mediated C6-Selective Dehydrogenative Heteroarylation of 2-Pyridones with 1,3-Azoles

Co-reporter:Riko Odani;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2014 Volume 126( Issue 40) pp:10960-10964

Publication Date(Web):

DOI:10.1002/ange.201406228

Abstract

A copper-mediated C6-selective dehydrogenative heteroarylation of 2-pyridones with 1,3-azoles has been developed. The reaction proceeded smoothly by twofold CH cleavage even in the absence of noble-metal catalysts. The observed site selectivity was directed by a pyridyl substituent on the nitrogen atom of the pyridone ring. This directing group was readily removed after the coupling event, thus leading to 2-pyridone derivatives with a free NH group. Moreover, in some cases, catalytic turnover of the Cu salt was also possible with the ideal terminal oxidant: molecular oxygen in air.

Copper-Mediated C6-Selective Dehydrogenative Heteroarylation of 2-Pyridones with 1,3-Azoles

Co-reporter:Riko Odani;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2014 Volume 53( Issue 40) pp:10784-10788

Publication Date(Web):

DOI:10.1002/anie.201406228

Abstract

Regioselective and Stereospecific Copper-Catalyzed Aminoboration of Styrenes with Bis(pinacolato)diboron and O-Benzoyl-N,N-dialkylhydroxylamines

Co-reporter:Naoki Matsuda ; Koji Hirano ; Tetsuya Satoh ;Masahiro Miura

Journal of the American Chemical Society 2013 Volume 135(Issue 13) pp:4934-4937

Publication Date(Web):March 15, 2013

DOI:10.1021/ja4007645

A Cu-catalyzed regioselective and stereospecific aminoboration of styrenes with bis(pinacolato)diboron and O-benzoyl-N,N-dialkylhydroxylamines that delivers the corresponding β-aminoalkylboranes in good yields has been developed. The Cu catalysis enables introduction of both amine and boron moieties to C–C double bonds simultaneously in a syn fashion. Moreover, the use of a chiral biphosphine ligand, (S,S)-Me-Duphos, provides a catalytic enantioselective route to optically active β-aminoalkylboranes.

Copper-Catalyzed Electrophilic Amination of Arylsilanes with Hydroxylamines

Co-reporter:Yuya Miki, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2013 Volume 15(Issue 1) pp:172-175

Publication Date(Web):December 20, 2012

DOI:10.1021/ol303222s

A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl]dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.

Copper-Mediated Dehydrogenative Biaryl Coupling of Naphthylamines and 1,3-Azoles

Co-reporter:Riko Odani, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2013 Volume 78(Issue 21) pp:11045-11052

Publication Date(Web):October 8, 2013

DOI:10.1021/jo402078q

A copper-mediated dehydrogenative biaryl cross-coupling of naphthylamines and 1,3-azoles has been developed. The key to its success is the introduction of N,N-bidentate coordination system based on the picolinamide directing group. The reaction proceeds smoothly without precious transition metal catalysts and provides highly π-extended heterobiaryls directly.

Nickel-Catalyzed Direct Alkylation of Heterocycles with -Bromo Carbonyl Compounds: C3-Selective Functionalization of 2-Pyridones

Co-reporter:Akihiro Nakatani;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Chemistry - A European Journal 2013 Volume 19( Issue 24) pp:7691-7695

Publication Date(Web):

DOI:10.1002/chem.201301350

Copper-Mediated CH/CH Biaryl Coupling of Benzoic Acid Derivatives and 1,3-Azoles

Co-reporter:Mayuko Nishino;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2013 Volume 52( Issue 16) pp:4457-4461

Publication Date(Web):

DOI:10.1002/anie.201300587

Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines

Co-reporter:Yuya Miki;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2013 Volume 52( Issue 41) pp:10830-10834

Publication Date(Web):

DOI:10.1002/anie.201304365

Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines

Co-reporter:Yuya Miki;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2013 Volume 125( Issue 41) pp:11030-11034

Publication Date(Web):

DOI:10.1002/ange.201304365

Copper-Mediated CH/CH Biaryl Coupling of Benzoic Acid Derivatives and 1,3-Azoles

Co-reporter:Mayuko Nishino;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2013 Volume 125( Issue 16) pp:4553-4557

Publication Date(Web):

DOI:10.1002/ange.201300587

A Concise Access to (Polyfluoroaryl)allenes by Cu-Catalyzed Direct Coupling with Propargyl Phosphates

Co-reporter:Akihiro Nakatani, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2012 Volume 14(Issue 10) pp:2586-2589

Publication Date(Web):May 2, 2012

DOI:10.1021/ol300886k

A copper-based catalyst system for the direct coupling of polyfluoroarenes with propargyl phosphates has been developed. The catalysis can provide a rapid and concise access to (polyfluoroaryl)allenes, which can be important building blocks for the synthesis of fluorinated functional materials.

Synthesis of N-Azolylindoles by Copper-Catalyzed C–H/N–H Coupling–Annulation Sequence of o-Alkynylanilines

Co-reporter:Yoshiro Oda, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2012 Volume 14(Issue 2) pp:664-667

Publication Date(Web):January 11, 2012

DOI:10.1021/ol203392r

A wide range of o-alkynylanilines undergo a copper-catalyzed direct C–H/N–H coupling with azoles followed by benzannulation to form the corresponding N-azolylindoles in good yields. The domino reaction proceeds effectively with molecular oxygen as the sole oxidant and provides a new dehydrogenative access to the titled compounds of interest in pharmaceutical and material sciences.

Copper-mediated oxidative direct C–C (hetero)aromatic cross-coupling

Co-reporter:Koji Hirano and Masahiro Miura

Chemical Communications 2012 vol. 48(Issue 87) pp:10704-10714

Publication Date(Web):18 Sep 2012

DOI:10.1039/C2CC34659A

Some new types of copper-mediated intermolecular oxidative direct C–C (hetero)aromatic cross-couplings are described. A combination of the simple CuCl2 salt and molecular oxygen allows 1,3-azoles to couple with terminal alkynes directly to form the corresponding heteroarylacetylenes. This direct version of Sonogashira-type coupling can be applied to the reaction with polyfluoroarenes. A copper acetate complex enables direct biaryl coupling between 2-arylazines and 1,3-azoles even in the absence of any palladium catalysts. Moreover, the Cu-based protocol can be extended to the coupling with indoles and pyrroles, in which a catalytic variant is also possible by using an ideal co-oxidant, atmospheric oxygen. On the other hand, a copper-promoted annulative direct coupling of o-alkynylphenols and -anilines with 1,3-azoles can provide a unique dehydrogenative approach to C3-azolylbenzoheteroles from nonhalogenated and nonmetalated starting materials. In addition, a related N-azolylindole synthesis from similar substrates is also disclosed.

An Annulative Electrophilic Amination Approach to 3-Aminobenzoheteroles

Co-reporter:Naoki Matsuda, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2012 Volume 77(Issue 1) pp:617-625

Publication Date(Web):December 1, 2011

DOI:10.1021/jo202207s

A copper-catalyzed annulative amination approach to 3-aminobenzofurans and -indoles from o-alkynylphenols and -anilines has been developed. The Cu-based catalysis is based on an umpolung, electrophilic amination with O-benzoyl hydroxylamines and enables the mild and convergent synthesis of various 3-aminobenzoheteroles of biological and pharmaceutical interest. Some mechanistic investigations and an application of this protocol to construction of more complex tricyclic framework are also described.

Nickel- and Cobalt-Catalyzed Direct Alkylation of Azoles with N-Tosylhydrazones Bearing Unactivated Alkyl Groups

Co-reporter:Tomoyuki Yao;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2012 Volume 124( Issue 3) pp:799-803

Publication Date(Web):

DOI:10.1002/ange.201106825

Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to -Amino Acids

Co-reporter:Naoki Matsuda;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2012 Volume 124( Issue 47) pp:11997-12001

Publication Date(Web):

DOI:10.1002/ange.201206755

Copper-Mediated and Copper-Catalyzed Cross-Coupling of Indoles and 1,3-Azoles: Double CH Activation

Co-reporter:Mayuko Nishino;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2012 Volume 124( Issue 28) pp:7099-7103

Publication Date(Web):

DOI:10.1002/ange.201201491

Copper-Catalyzed Amination of Arylboronates with N,N-Dialkylhydroxylamines

Co-reporter:Naoki Matsuda;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2012 Volume 124( Issue 15) pp:3702-3705

Publication Date(Web):

DOI:10.1002/ange.201108773

Copper-Mediated and Copper-Catalyzed Cross-Coupling of Indoles and 1,3-Azoles: Double CH Activation

Co-reporter:Mayuko Nishino;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2012 Volume 51( Issue 28) pp:6993-6997

Publication Date(Web):

DOI:10.1002/anie.201201491

Nickel- and Cobalt-Catalyzed Direct Alkylation of Azoles with N-Tosylhydrazones Bearing Unactivated Alkyl Groups

Co-reporter:Tomoyuki Yao;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2012 Volume 51( Issue 3) pp:775-779

Publication Date(Web):

DOI:10.1002/anie.201106825

Copper-Catalyzed Amination of Arylboronates with N,N-Dialkylhydroxylamines

Co-reporter:Naoki Matsuda;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2012 Volume 51( Issue 15) pp:3642-3645

Publication Date(Web):

DOI:10.1002/anie.201108773

Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to -Amino Acids

Co-reporter:Naoki Matsuda;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2012 Volume 51( Issue 47) pp:11827-11831

Publication Date(Web):

DOI:10.1002/anie.201206755

Copper-Mediated Intermolecular Direct Biaryl Coupling

Co-reporter:Masanori Kitahara ; Nobuyoshi Umeda ; Koji Hirano ; Tetsuya Satoh ;Masahiro Miura

Journal of the American Chemical Society 2011 Volume 133(Issue 7) pp:2160-2162

Publication Date(Web):January 26, 2011

DOI:10.1021/ja111401h

Copper-mediated intermolecular direct biaryl coupling of arylazines and azoles via dual C−H bond cleavage proceeds even without palladium catalysts. The reaction system shows the high potential of copper salts in direct C−H arylation chemistry and provides a new approach to biaryl motifs, which are ubiquitous in pharmaceuticals and functional materials.

Copper-Mediated Annulative Direct Coupling of o-Alkynylphenols with Oxadiazoles: A Dehydrogenative Cascade Construction of Biheteroaryls

Co-reporter:Hitoshi Hachiya, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2011 Volume 13(Issue 12) pp:3076-3079

Publication Date(Web):May 17, 2011

DOI:10.1021/ol200975j

A copper-mediated annulative direct coupling of o-alkynylphenols with 1,3,4-oxadiazoles proceeds smoothly even under ambient conditions to afford the corresponding biheteroaryls. The reaction system represents a new avenue for the construction of biheteroaryl molecules of interest in their biological and physical properties.

Copper-Catalyzed Direct Amination of Electron-Deficient Arenes with Hydroxylamines

Co-reporter:Naoki Matsuda, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

Organic Letters 2011 Volume 13(Issue 11) pp:2860-2863

Publication Date(Web):May 6, 2011

DOI:10.1021/ol200855t

The C–H amination of electron-deficient arenes such as polyfluoroarenes and azole compounds with O-acylated hydroxylamines effectively proceeds in the presence of a copper catalyst even at room temperature to provide the corresponding anilines and aminoazoles in good yields.

A remarkable effect of ionic liquids in transition-metal-free aerobic oxidation of benzylic alcohols

Co-reporter:Yoshiro Oda, Koji Hirano, Tetsuya Satoh, Susumu Kuwabata, Masahiro Miura

Tetrahedron Letters 2011 Volume 52(Issue 41) pp:5392-5394

Publication Date(Web):12 October 2011

DOI:10.1016/j.tetlet.2011.08.053

The transition-metal-free aerobic oxidation of benzylic alcohols is uniquely accelerated by a 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6)/PhCF3 biphasic system and Cs2CO3 to afford the corresponding ketones in good yields. The reaction system is also applicable to an oxidative cross-esterification of primary benzyl alcohols with a higher aliphatic alcohol.

Copper-Catalyzed Oxidative Direct Cyclization of N-Methylanilines with Electron-Deficient Alkenes Using Molecular Oxygen

Co-reporter:Mayuko Nishino, Koji Hirano, Tetsuya Satoh, and Masahiro Miura

The Journal of Organic Chemistry 2011 Volume 76(Issue 15) pp:6447-6451

Publication Date(Web):June 30, 2011

DOI:10.1021/jo2011329

The oxidative direct cyclizaion of N-methylanilines with electron-deficient alkenes involving maleimides and benzylidene malononitriles through sp3 and sp2 C–H bond cleavage proceeds effectively under a CuCl2/O2 catalysis to provide the corresponding tetrahydroquinolines in good yields.

Stereospecific Copper-Catalyzed CH Allylation of Electron-Deficient Arenes with Allyl Phosphates

Co-reporter:Tomoyuki Yao;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie International Edition 2011 Volume 50( Issue 13) pp:2990-2994

Publication Date(Web):

DOI:10.1002/anie.201007733

Stereospecific Copper-Catalyzed CH Allylation of Electron-Deficient Arenes with Allyl Phosphates

Co-reporter:Tomoyuki Yao;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Angewandte Chemie 2011 Volume 123( Issue 13) pp:3046-3050

Publication Date(Web):

DOI:10.1002/ange.201007733

Palladium- and Nickel-Catalyzed Direct Alkylation of Azoles with Unactivated Alkyl Bromides and Chlorides

Co-reporter:Tomoyuki Yao;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

Chemistry - A European Journal 2010 Volume 16( Issue 41) pp:12307-12311

Publication Date(Web):

DOI:10.1002/chem.201001631

Oxidative NickelAir Catalysis in CH Arylation: Direct Cross-Coupling of Azoles with Arylboronic Acids using Air as Sole Oxidant

Co-reporter:Hitoshi Hachiya;Dr. Koji Hirano;Dr. Tetsuya Satoh ;Dr. Masahiro Miura

ChemCatChem 2010 Volume 2( Issue 11) pp:1403-1406

Publication Date(Web):

DOI:10.1002/cctc.201000223

Copper-Mediated Oxidative Coupling of Benzamides with Maleimides via Directed C–H Cleavage

Co-reporter:Wataru Miura; Koji Hirano;Masahiro Miura

Organic Letters () pp:

Publication Date(Web):July 30, 2015

DOI:10.1021/acs.orglett.5b01940

A Cu(OAc)2/Cy2NMe-mediated oxidative direct coupling of benzamides with maleimides has been developed. The aromatic C–H alkenylation with the aid of an 8-aminoquinoline-based bidentate directing group is followed by an intramolecular aza-Michael-type addition to form the isoindolone-incorporated spirosuccinimides, which are of potent interest in medicinal chemistry.

Copper-mediated oxidative direct C–C (hetero)aromatic cross-coupling

Co-reporter:Koji Hirano and Masahiro Miura

Chemical Communications 2012 - vol. 48(Issue 87) pp:NaN10714-10714

Publication Date(Web):2012/09/18

DOI:10.1039/C2CC34659A