Faculty Profiles - ISHIHARA Kazuaki

Radical Cation [4+2] Cycloaddition of Non-Conjugated Tetrasubstituted Alkenes by an FeCl3/AgSbF6 Co-Initiator Open Access

Shuhei Ohmura, Ryosuke Isogai, Kazuaki Ishihara

Asian Journal of Organic Chemistry Vol. 10 ( 10 ) page： 2534 - 2537 2021.10

Language：English Publishing type：Research paper (scientific journal) Publisher：John Wiley and Sons Inc

Radical cation [4+2] cycloaddition is an alternative strategy for constructing various six-membered rings that cannot be easily accessed by thermal [4+2] cycloaddition. Here, we developed an FeCl3/AgSbF6 co-initiator to promote radical cation [4+2] cycloaddition of non-conjugated tetrasubstituted alkenes with 2,3-dimethyl-1,3-butadiene. In the presence of 10 mol% of FeCl3 and 30 mol% of AgSbF6, the reaction proceeded smoothly in MeCN to provide the cycloadducts from tetrasubstituted alkenes having an electron-rich aromatic group, which improved the yield. We demonstrate the efficiency of an FeCl3/AgSbF6 co-initiator by comparing our finding to the results with previously reported iron(III) initiators in an investigation of the substrate scope. In addition, a kinetic study was conducted to elucidate the detailed reaction mechanism, in which the rate-determining step can be facilitated by intramolecular single electron transfer.

DOI： 10.1002/ajoc.202100473

Enantio- And Diastereoselective Carbonyl-Ene Cyclization-Acetalization Tandem Reaction Catalyzed by Tris(pentafluorophenyl)borane-Assisted Chiral Phosphoric Acids Open Access

触媒的ペプチド合成の最前線 Invited Reviewed

石原一彰

ファルマシア Vol. 57 ( 9 ) page： 804 - 809 2021.9

光学活性ビナフチルジスルホン酸(BINSA)を用いる精密分子触媒設計と不斉合成 Invited Reviewed

石原一彰

硫酸と工業 Vol. 74 ( 6 ) page： 71 - 85 2021.6

Hideyuki Ishihara, Jianhao Huang, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara

ACS Catalysis Vol. 11 ( 10 ) page： 6121 - 6127 2021.5

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

Highly enantio- and diastereoselective carbonyl-ene cyclization was developed with the use of chiral Lewis acid-assisted chiral Brønsted acid (LBA) catalysts, which were prepared in situ from both sterically demanding tris(pentafluorophenyl)borane and chiral phosphoric acids. Along with the performance of standard carbonyl-ene cyclizations, carbonyl-ene cyclization-acetalization tandem reactions with the use of additional aldehydes were demonstrated with high enantio- and diastereoselectivities. On the basis of mechanistic examinations, a stepwise reaction pathway via tertiary carbocation intermediates involving possible transition states is proposed.

DOI： 10.1021/acscatal.1c01242

Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives Open Access

Hiroyuki Hayashi, Shotaro Yasukochi, Tatsuhiro Sakamoto, Manabu Hatano, Kazuaki Ishihara

The Journal of Organic Chemistry Vol. 86 ( 7 ) page： 5197 - 5212 2021.4

Synthesis of chiral organoiodine catalyst for enantioselective oxidative dearomatization reactions: N,N'-(2S,2'S)-(2-iodo-1,3-phenylene)bis(oxy)bis(propane-2,1-diyl)bis(2,4,6-trimethylbenzamide) Invited Reviewed

Muhammet Uyanik, Shinichi Ishizaki and Kazuaki Ishihara

Org. Synth. Vol. 98 page： 1 - 7 2021.2

Reusable Silica‐Supported Ammonium BINSate Catalysts for Enantio‐ and Diastereoselective Friedel–Crafts‐Type Double Aminoalkylation of N ‐Alkylpyrroles with Aldimines Open Access

Manabu Hatano, Xue Zhao, Takuya Mochizuki, Kyogo Maeda, Ken Motokura, Kazuaki Ishihara

Asian Journal of Organic Chemistry Vol. 10 ( 2 ) page： 360 - 365 2021.2

Chemoselective Transesterification of Methyl (Meth)acrylates Catalyzed by Sodium(I) or Magnesium(II) Aryloxides Open Access

Jie Qi Ng, Hiro Arima, Takuya Mochizuki, Kohei Toh, Kai Matsui, Manussada Ratanasak, Jun-Ya Hasegawa, Manabu Hatano, Kazuaki Ishihara

ACS Catalysis Vol. 11 ( 1 ) page： 199 - 207 2021.1

Chiral organoiodine-catalyzed enantioselective oxidative dearomatization of phenols Open Access

Muhammet Uyanik, Shinichi Ishizaki, Kazuaki Ishihara

Organic Syntheses Vol. 98 page： 28 - + 2021

Synthesis of chiral organoiodine catalyst for enantioselective oxidative dearomatization reactions: N,n'-(2s,2's)-(2-iodo-1,3-phenylene)bis(oxy)bis(propane-2,1-diyl)bis(2,4,6-trimethylbenzamide) Open Access

Muhammet Uyanik, Shinichi Ishizaki, Kazuaki Ishihara

Organic Syntheses Vol. 98 page： 1 - + 2021

Enantioselective Aza-Friedel–Crafts Reaction of Indoles and Pyrroles Catalyzed by Chiral C1-Symmetric Bis(phosphoric Acid) Open Access

Manabu Hatano, Kohei Toh, Kazuaki Ishihara

Organic Letters Vol. 22 ( 24 ) page： 9614 - 9620 2020.12

Reusable silica-supported ammonium BINSate catalysts for enantio- and diastereoselective Friedel–Crafts-type double aminoalkylation of N-alkylpyrroles with aldimines Invited Reviewed

Manabu Hatano, Xue Zhao, Takuya Mochizuki, Kyogo Maeda, Ken Motokura, Kazuaki Ishihara

Asian J. Org. Chem. Vol. 10 ( 2 ) page： 360 - 365 2020.12

I+/TBHP catalysis for the tandem oxidative cyclization to indolo[2,3-b]quinolines Invited Reviewed

Muhammet Uyanik, Hiroki Tanaka, Kazuaki Ishihara

Asian J. Org. Chem. Vol. 10 ( 1 ) page： 164 - 169 2020.11

Multifactor Control of Vinyl Monomer Sequence, Molecular Weight, and Tacticity via Iterative Radical Additions and Olefin Metathesis Reactions Open Access

Masato Miyajima, Kotaro Satoh, Takahiro Horibe, Kazuaki Ishihara, Masami Kamigaito

Journal of the American Chemical Society Vol. 142 ( 44 ) page： 18955 - 18962 2020.11

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

Monomer sequence control in terms of a single monomer unit, particularly in vinyl polymers, is one of the largest challenges in polymer chemistry. Furthermore, multifactor control of monomer sequence, molecular weight, and stereoregularity is an ultimate goal. In this work, we propose a strategy to prepare C-C main-chain sequence-regulated polymers with controlled molecular weights from vinyl monomers via a combination of iterative atom transfer radical additions and olefin metathesis reactions. This strategy enabled the synthesis of sequence-regulated polymers with exact styrene-acrylate-styrene sequences in the C-C main chains, controlled molecular weights of up to 104, and stereoregularities varying with syndiotacticity, isotacticity, and heterotacticity. The utility of this strategy is further demonstrated by formation of block copolymers consisting of sequence-regulated vinyl polymer segments by combining living ROMP of norbornene derivatives.

DOI： 10.1021/jacs.0c09289

Hypoiodite-Catalyzed Chemoselective Tandem Oxidation of Homotryptamines to Peroxy- And Epoxytetrahydropyridoindolenines Open Access

Muhammet Uyanik, Hiroki Tanaka, Kazuaki Ishihara

Organic Letters Vol. 22 ( 20 ) page： 8049 - 8054 2020.10

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

We developed the hypoiodite-catalyzed tandem dearomative peroxycyclization of homotryptamine derivatives to peroxytetrahydropyridoindolenines under mild conditions. During the course of a mechanistic study, we found that a tandem oxidative cyclization/epoxidation as an unexpected reaction proceeded in the presence of TEMPO as an additive. Intramolecular oxidative aminocyclization of homotryptamines at the C-2 position would give tetrahydropyridoindole, a common intermediate for both reactions. Control experiments suggested that while oxidative coupling with TBHP at the C-3 position might afford peroxyindolenines, a preferential electrophilic addition of TEMPO+, which might be generated in situ by the hypoiodite-catalyzed oxidation of TEMPO, at C-3 position followed by elimination and epoxidation might give epoxyindolenines. This serendipitous finding prompted us to develop a chemoselective divergent synthesis of peroxy- and epoxyindolenines by simple modification of the reaction conditions.

DOI： 10.1021/acs.orglett.0c03001

Enantio- and Site-Selective α-Fluorination of N-Acyl 3,5-Dimethylpyrazoles Catalyzed by Chiral π–CuII Complexes

Kazuaki Ishihara, Kazuki Nishimura, Katsuya Yamakawa

Angewandte Chemie - International Edition Vol. 59 ( 40 ) page： 17641 - 17647 2020.9

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

Catalytic enantioselective α-fluorination reactions of carbonyl compounds are among the most powerful and efficient synthetic methods for constructing optically active α-fluorinated carbonyl compounds. Nevertheless, α-fluorination of α-nonbranched carboxylic acid derivatives is still a big challenge because of relatively high pKa values of their α-hydrogen atoms and difficulty of subsequent synthetic transformation without epimerization. Herein we show that chiral copper(II) complexes of 3-(2-naphthyl)-l-alanine-derived amides are highly effective catalysts for the enantio- and site-selective α-fluorination of N-(α-arylacetyl) and N-(α-alkylacetyl) 3,5-dimethylpyrazoles. The substrate scope of the transformation is very broad (25 examples including a quaternary α-fluorinated α-amino acid derivative). α-Fluorinated products were converted into the corresponding esters, secondary amides, tertiary amides, ketones, and alcohols with almost no epimerization in high yield.

DOI： 10.1002/anie.202007403

Enantioselective 1,4-Addition Reaction of α,β-Unsaturated Carboxylic Acids with Cycloalkanones Using Cooperative Chiral Amine–Boronic Acid Catalysts

Takahiro Horibe, Takashi Hazeyama, Yuto Nakata, Kazuki Takeda, Kazuaki Ishihara

Angewandte Chemie - International Edition Vol. 59 ( 39 ) page： 17256 - 17260 2020.9

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

An enantioselective 1,4-addition of α,β-unsaturated carboxylic acids with cycloalkanones has been developed by using chiral amine–boronic acid cooperative catalysts. In the presence of a chiral amine and boronic acid, cycloalkanones and carboxylic acids are activated as chiral enamines and mixed anhydrides, respectively. The corresponding 1,4-adducts are obtained in high yield with high enantioselectivity. Furthermore, subsequent oxylactonization of the 1,4-adducts gives spirolactones with high diastereoselectivity.

DOI： 10.1002/anie.202007639

Chemo- and Enantioselective Oxidative α-Azidation of Carbonyl Compounds

Muhammet Uyanik, Naoto Sahara, Mayuko Tsukahara, Yuhei Hattori, Kazuaki Ishihara

Angewandte Chemie - International Edition Vol. 59 ( 39 ) page： 17110 - 17117 2020.9

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

We report high-performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α-azidation of carbonyl compounds by using sodium azide under biphasic neutral phase-transfer conditions. To induce higher reactivity especially for the α-azidation of 1,3-dicarbonyl compounds, we designed a structurally compact isoindoline-derived quaternary ammonium iodide catalyst bearing electron-withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical-trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late-stage α-azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α-azidation of 1,3-dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.

DOI： 10.1002/anie.202007552

One-Pot Tandem Michael Addition/Enantioselective Conia-Ene Cyclization Mediated by Chiral Iron(III)/Silver(I) Cooperative Catalysis

Chemo‐ and Enantioselective Oxidative α‐Azidation of Carbonyl Compounds

Muhammet Uyanik, Naoto Sahara, Mayuko Tsukahara, Yuhei Hattori, Kazuaki Ishihara

Angewandte Chemie Vol. 132 ( 39 ) page： 17258 - 17265 2020.9

Takahiro Horibe, Masato Sakakibara, Rin Hiramatsu, Kazuki Takeda, Kazuaki Ishihara

Angewandte Chemie - International Edition Vol. 59 ( 38 ) page： 16470 - 16474 2020.9

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

The first one-pot tandem Michael addition/enantioselective Conia-ene cyclization of N-protected prop-2-yn-1-amines with 2-methylene-3-oxoalkanoates promoted by chiral iron(III)/silver(I) cooperative catalysts has been developed. Alkyl 4-methylenepyrrolidine-3-acyl-3-carboxylates, which can be transformed into β-proline derivatives, are obtained in high yield with high enantioselectivity.

DOI： 10.1002/anie.202007180

Chemoselective oxidative generation of ortho-quinone methides and tandem transformations

Halogen-Bonding Interaction between I2and N-Iodosuccinimide in Lewis Base-Catalyzed Iodolactonization Open Access

Takahiro Horibe, Yasutaka Tsuji, Kazuaki Ishihara

Organic Letters Vol. 22 ( 12 ) page： 4888 - 4892 2020.6

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

The halogen-bonding interaction between I2 and N-iodosuccinimide (NIS) stabilized by a Lewis base (LB) has been explored. 1H NMR, nuclear Overhauser effect (NOE), and diffusion-ordered NMR spectroscopy (DOSY) suggest the generation of a 1:1:1 assembly, LB-I2-NIS. In contrast, when N-iodotrifluoromethanesulfonimide (INTf2) is used instead of NIS, LB-I5+-LB is generated. On the basis of these results in combination with density functional theory (DFT) calculations, we propose a mechanism for the formation of I2-NIS and the subsequent generation of an active iodinating species LB-I+.

DOI： 10.1021/acs.orglett.0c01735

One-pot Michael addition-enantioselective Conia-ene cyclization tandem reaction induced through chiral iron(III)-silver(I) cooperative catalysis Invited Reviewed

Takahiro Horibe, Masato Sakakibara, Rin Hiramatsu, Kazuki Takeda, Kazuaki Ishihara

Angew. Chem. Int. Ed. 2020.6

Muhammet Uyanik, Kohei Nishioka, Ryutaro Kondo, Kazuaki Ishihara

Nature Chemistry Vol. 12 ( 4 ) page： 353 - + 2020.4

Language：English Publishing type：Research paper (scientific journal) Publisher：Nature Research

ortho-Quinone methides are useful transient synthetic intermediates in organic synthesis. These species are most often generated in situ by the acid- or base-mediated transformation of phenols that have been pre-functionalized at a benzylic position, or by biomimetic oxidation of the corresponding ortho-alkylphenols with metal oxidants or transition-metal complexes. Here we describe a method for the transition-metal-free oxidative generation of o-QMs from ortho-alkylarenols, using hypoiodite catalysis under nearly neutral conditions, which can then be applied in one-pot tandem reactions. This method for the chemoselective oxidative generation of ortho-quinone methides may prove superior to previous methods with respect to environmental issues and scope, and can be applied to various tandem reactions such as inter- or intramolecular [4 + 2] cycloaddition, oxa-6π-electrocyclization, conjugate addition and spiroepoxidation. [Figure not available: see fulltext.].

DOI： 10.1038/s41557-020-0433-4

Visual Feedback Control of a Rat Ankle Angle Using a Wirelessly Powered Two-Channel Neurostimulator Open Access

Takeuchi, M; Watanabe, K; Ishihara, K; Miyamoto, T; Tokutake, K; Saeki, S; Aoyama, T; Hasegawa, Y; Kurimoto, S; Hirata, H

SENSORS Vol. 20 ( 8 ) 2020.4

Cationic Iron(III) Salt as an Initiator for Radical Cation-induced [4+2] Cycloaddition

Takahiro Horibe, Shuhei Ohmura, Kei Katagiri, Kazuaki Ishihara

Asian Journal of Organic Chemistry Vol. 9 ( 3 ) page： 395 - 398 2020.3

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

We developed a cationic iron(III) salt initiator for radical cation-induced [4+2] cycloaddition. Fe(OTf)3 [or Fe(ClO4)3] behaves as a highly active oxidant for both electron-deficient and electron-rich dienophiles. The scope of substrates is much broader than with FeCl3 reported previously. With highly active Fe(OTf)3, we demonstrate a formal total synthesis of Heitziamide A.

DOI： 10.1002/ajoc.201900749

Radical-Cation-Induced Crossed [2+2] Cycloaddition of Electron-Deficient Anetholes Initiated by Iron(III) Salt Open Access

Takahiro Horibe, Kei Katagiri, Kazuaki Ishihara

Advanced Synthesis and Catalysis Vol. 362 ( 4 ) page： 960 - 963 2020.2

Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH Verlag

Radical cation-induced crossed [2+2] cycloaddition of electron-deficient anetholes was developed with the use of Fe(OTf)3 as an initiator. Various 1,2-diarylcyclobutanes can be synthesized in high yields with high diastereoselectivity from electron-deficient anetholes, which have been less explored using conventional methods. This practical reaction system can be used for a decagram-scale reaction (12 gram), in which the resulting product can be transformed to 1,2-dicarbonyl compounds. (Figure presented.).

DOI： 10.1002/adsc.201901337

Chemoselective Oxidative Spiroetherification and Spiroamination of Arenols Using I+/Oxone Catalysis

Muhammet Uyanik, Naoto Sahara, Outa Katade, Kazuaki Ishihara

Organic Letters Vol. 22 ( 2 ) page： 560 - 564 2020.1

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

We developed a chemoselective oxidative dearomative spiroetherification and spiroamination of arenols using I+/oxone catalysis. The intramolecular dearomative C-O and C-N couplings proceeded much more efficiently under slightly acidic conditions to give the corresponding spiro adducts in higher yields compared with previous methods using transition metal or hypervalent iodine catalysts. Control experiments suggested that both hypoiodous acid and iodine might be active species for these reactions.

DOI： 10.1021/acs.orglett.9b04324

Initiators for radical cation-induced [2 + 2]- and [4 + 2]-cycloadditions of electron-rich Alkenes Open Access

Takahiro Horibe, Kazuaki Ishihara

Chemistry Letters Vol. 49 ( 1 ) page： 107 - 113 2020.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Chemical Society of Japan

The radical cation-induced [2 + 2]- and [4 + 2]-cycloadditions of electron-rich alkenes afford cyclobutanes and cyclohexenes, which are used in the synthesis of natural products. The key intermediate is the alkene radical cation, which is generated from alkene by a one-electron oxidant. These cycloadditions have attracted renewed attention thanks to the recent development of initiators, such as a chemical oxidant, an electrochemical method and photoredox catalysts. This Highlight Review summarizes these initiators for [2 + 2]- and [4 + 2]-cycloadditions that leverage the generation of the alkene radical cation.

DOI： 10.1246/cl.190790

An enantioselective oxidative coupling reaction of 2-naphthol derivatives catalyzed by chiral diphosphine oxide-iron(ii) complexes Open Access

Takahiro Horibe, Keita Nakagawa, Takashi Hazeyama, Kazuki Takeda, Kazuaki Ishihara

Chemical Communications Vol. 55 ( 91 ) page： 13677 - 13680 2019.11

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry

An enantioselective oxidative coupling of 2-naphthol derivatives is developed with the use of chiral Fe(ii)-diphosphine oxide complexes. Optically active 1,1-bi-2-naphthol derivatives can be synthesized in high yields when a 2 : 1 complex of (S)-xylyl-iPrO-BIPHEP-oxide and Fe(OTf)2 is used in the presence of t-butyl hydroperoxide as an oxidant. The non-linear effect, X-ray crystal structure and ESI-MS suggest that a 2 : 1 complex of (S)-xylyl-iPrO-BIPHEP-oxide and Fe(OTf)2 is a pre-catalyst for a Fe(iii)/Fe(iv) redox cycle.

DOI： 10.1039/c9cc07834g

High-performance ammonium hypoiodite/Oxone catalysis for enantioselective oxidative dearomatization of arenols Reviewed

Muhammet Uyanik, Takehiro Kato, Naoto Sahara, Outa Katade, Kazuaki Ishihara

ACS Catal. Vol. 9 ( 12 ) page： 11619-11626 2019.11

ホウ素Lewis酸—キラルリン酸複合触媒を用いるマルチ選択的[2+2]/[4+2]付加環化反応 Invited Reviewed

波多野学，石原一彰

化学工業 Vol. 70 ( 9 ) page： 634-642 2019.9

Highly Active Chiral Dilithium(I) Binaphthyldisulfonate Catalysts for Enantio- and Chemoselective Strecker-Type Reactions

Manabu Hatano, Kosuke Nishio, Takuya Mochizuki, Keisuke Nishikawa, Kazuaki Ishihara

ACS Catalysis Vol. 9 ( 9 ) page： 8178 - 8186 2019.9

Highly active chiral dilithium(I) binaphthyldisulfonate catalysts for enantio- and chemoselective Strecker-type reactions

Manabu Hatano, Kosuke Nishio, Takuya Mochizuki, Keisuke Nishikawa, Kazuaki Ishihara

ACS Catal. Vol. 9 ( 9 ) page： 8178-8196 2019.7

Tris(pentafluorophenyl)borane‐Assisted Chiral Phosphoric Acid Catalysts for Enantioselective Inverse‐Electron‐Demand Hetero‐Diels‐Alder Reaction of α,β‐Substituted Acroleins Open Access

Manabu Hatano, Tatsuhiro Sakamoto, Takuya Mochizuki, Kazuaki Ishihara

Asian Journal of Organic Chemistry Vol. 8 ( 7 ) page： 1061 - 1066 2019.7

Front Cover: Tris(pentafluorophenyl)borane‐Assisted Chiral Phosphoric Acid Catalysts for Enantioselective Inverse‐Electron‐Demand Hetero‐Diels‐Alder Reaction of α,β‐Substituted Acroleins (Asian J. Org. Chem. 7/2019)

Manabu Hatano, Tatsuhiro Sakamoto, Takuya Mochizuki, Kazuaki Ishihara

Asian Journal of Organic Chemistry Vol. 8 ( 7 ) page： 918 - 918 2019.7

塩化鉄(III)を用いた芳香族ラジカルカチオンの単離と反応性 Invited Reviewed

堀部貴大，大村修平，石原一彰

ケミカルエンジニヤリング Vol. 64 ( 5 ) page： 297-304 2019.5

Ammonium Hypoiodite-catalyzed Oxidative Dearomatizative Azidation of Arenols Reviewed

Muhammet Uyanik, Kohei Nishioka, Kazuaki Ishihara

Chem. Lett. Vol. 48 ( 4 ) page： 353 - 356 2019.4

Enantioselective [1,3] O-to-C rearrangement: dearomatization of alkyl 2-allyloxy/benzyloxy-1/3-naphthoates catalyzed by a chiral pi-Cu(II) complex Open Access

Yao Lu, Ishihara Kazuaki

CHEMICAL SCIENCE Vol. 10 ( 8 ) page： 2259 - 2263 2019.2

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl3 Reviewed Open Access

Takahiro Horibe, Shuhei Ohmura, Kazuaki Ishihara

Journal of the American Chemical Society Vol. 141 ( 5 ) page： 1877 - 1881 2019.2

Ammonium hypoiodite-catalyzed oxidative dearomatizative azidation of arenols Reviewed

Muhammet Uyanik, Kohei Nishioka, Kazuaki Ishihara

Chem. Lett. Vol. 48 ( 4 ) page： 353-356 2019.1

Regioselective oxidative chlorination of arenols using NaCl and oxone Invited Reviewed Open Access

Muhammet Uyanik, Naoto Sahara, Kazuaki Ishihara

Eur. J. Org. Chem. Vol. 2019 ( 1 ) page： 27 - 31 2019.1

Front Cover: Regioselective Oxidative Chlorination of Arenols Using NaCl and Oxone (Eur. J. Org. Chem. 1/2019) Reviewed

Muhammet Uyanik, Naoto Sahara, Kazuaki Ishihara

European Journal of Organic Chemistry Vol. 2019 ( 1 ) page： 1 - 1 2019.1

Author Correction: Pentamethylcyclopentadienyl rhodium(iii)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization Reviewed Open Access

Shun Satake, Takumaru Kurihara, Keisuke Nishikawa, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara, Tatsuhiko Yoshino, Shigeki Matsunaga

Nature Catalysis Vol. 2 ( 1 ) page： 94 2019.1

[解説] “デザイン型Brønsted酸触媒を用いるエナンチオ選択的アザ-Friedel-Crafts反応” Invited Reviewed

波多野学，石原一彰

触媒 Vol. 61 ( 5 ) page： 298-304 2019

デザイナーC2対称ジアミド型キラルヨードアレーン触媒

ウヤヌクムハメット、石原一彰

TCIメール ( 182 ) page： 2-16 2019

Designer C2-symmetric Chiral Diamide-type Organoiodine Catalysts Invited Reviewed

Muhammet Uyanik and Kazuaki Ishihara

TCIMAIL ( 182 ) page： 2-14 2019

Synthesis of 1,1-Spirobiindane-7,7-Disulfonic Acid and Disulfonimide: Application for Catalytic Asymmetric Aminalization Open Access

Kurihara Takumaru, Satake Shun, Hatano Manabu, Ishihara Kazuaki, Yoshino Tatsuhiko, Matsunaga Shigeki

CHEMISTRY-AN ASIAN JOURNAL Vol. 13 ( 17 ) page： 2378 - 2381 2018.9

Enantioselective aza-Friedel-Crafts reaction of furan with alpha-ketimino esters induced by a conjugated double hydrogen bond network of chiral bis(phosphoric acid) catalysts Reviewed Open Access

Manabu Hatano, Haruka Okamoto, Taro Kawakami, Kohei Toh, Hidefumi Nakatsuji, Akira Sakakura, Kazuaki Ishihara

CHEMICAL SCIENCE Vol. 9 ( 30 ) page： 6361 - 6367 2018.8

Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

Chiral C-2- and C-1-symmetric BINOL-derived bis(phosphoric acid) catalysts, which have OP(=O)(OH)(2)/OP(=O)(OH)(OR) moieties at the 2,2 0 - positions, were developed and used for the enantioselective azaFriedel-Crafts reaction of 2-methoxyfuran with alpha-ketimino esters for the first time. The intramolecular conjugated double hydrogen bond network is a key to increasing the Bronsted acidity and preventing deactivation of the catalysts. Highly functionalized alpha-amino acid derivatives with a chiral quaternary carbon center could be transformed into versatile optically active N- and O-heterocycles and an a- arylsubstituted serine.

DOI： 10.1039/c8sc02290a

Pentamethylcyclopentadienyl rhodium(III)/chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization Reviewed

ホウ素触媒でカルボン酸を自在に変換する！　アシロキシボラン中間体を鍵とするエナンチオ選択的変換反応

堀部貴大、石原一彰

化学 Vol. 73 ( 8 ) page： 25-28 2018.8

Shun Satake, Takumaru Kurihara, Keisuke Nishikawa, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara, Tatsuhiko Yoshino, Shigeki Matsunaga

Nat. Catal. Vol. 1 ( 8 ) page： 585 - 591 2018.8

Thiourea–I2 as Lewis base–Lewis acid cooperative catalysts for iodochlorination of alkene with in situ-generated I–Cl Reviewed Open Access

Takahiro Horibe, Yasutaka Tsuji, Kazuaki Ishihara

ACS Catal. Vol. 8 ( 7 ) page： 6362 - 6366 2018.7

Preface Invited Open Access

Ishihara Kazuaki

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN Vol. 76 ( 6 ) page： 563-563 2018.6

The: Ortho -substituent on 2,4-bis(trifluoromethyl)phenylboronic acid catalyzed dehydrative condensation between carboxylic acids and amines Reviewed Open Access

Ke Wang, Yanhui Lu, Kazuaki Ishihara

Chemical Communications Vol. 54 ( 43 ) page： 5410 - 5413 2018.5

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry

2,4-Bis(trifluoromethyl)phenylboronic acid is a highly effective catalyst for dehydrative amidation between carboxylic acids and amines. Mechanistic studies suggest that a 2:2 mixed anhydride is expected to be the only active species, and the ortho-substituent of boronic acid plays a key role in preventing the coordination of amines to the boron atom of the active species, thus accelerating the amidation. This catalyst works for α-dipeptide synthesis.

DOI： 10.1039/c8cc02558d

Enantioselective Halo-oxy- and Halo-azacyclizations Induced by Chiral Amidophosphate Catalysts and Halo-Lewis Acids Reviewed

Yanhui Lu, Hidefumi Nakatsuji, Yukimasa Okumura, Lu Yao, Kazuaki Ishihara

Journal of the American Chemical Society Vol. 140 ( 19 ) page： 6039 - 6043 2018.5

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

Catalytic enantioselective halocyclization of 2-alkenylphenols and enamides have been achieved through the use of chiral amidophosphate catalysts and halo-Lewis acids. Density functional theory calculations suggested that the Lewis basicity of the catalyst played an important role in the reactivity and enantioselectivity. The resulting chiral halogenated chromans can be transformed to α-Tocopherol, α-Tocotrienol, Daedalin A and Englitazone in short steps. Furthermore, a halogenated product with an unsaturated side chain may provide polycyclic adducts under radical cyclization conditions.

DOI： 10.1021/jacs.8b02607

Metal-free transesterification catalyzed by tetramethylammonium methyl carbonate Reviewed Open Access

Manabu Hatano, Yuji Tabata, Yurika Yoshida, Kohei Toh, Kenji Yamashita, Yoshihiro Ogura, Kazuaki Ishihara

Green Chemistry Vol. 20 ( 6 ) page： 1193 - 1198 2018.3

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry

Environmentally benign metal-free tetramethylammonium methyl carbonate is effective as a catalyst for the chemoselective, scalable, and reusable transesterification of various esters and alcohols in common organic solvents. In situ-generated highly active species, tetramethylammonium alkoxides, can greatly avoid self-decomposition at ≤110 °C, and are reusable. In particular, chelating substrates, such as amino alcohols, diols, triols, sugar derivatives, alkaloids, α-amino acid esters, etc., which deactivate conventional metal salt catalysts, can be used. A 100 gram scale biodiesel production was also demonstrated.

DOI： 10.1039/c7gc03858e

Enantioselective Aza-Friedel-Crafts Reaction of Indoles with Ketimines Catalyzed by Chiral Potassium Binaphthyldisulfonates Reviewed

ボロン酸触媒を用いるアミド縮合反応 Invited Reviewed

石原一彰

PETROTECH Vol. 41 ( 1 ) page： 16-19 2018.1

Manabu Hatano, Takuya Mochizuki, Keisuke Nishikawa, Kazuaki Ishihara

ACS Catalysis Vol. 8 ( 1 ) page： 349 - 353 2018.1

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

The enantioselective aza-Friedel-Crafts reaction of indoles with low-reactive ketimines has been developed in the presence of a chiral monopotassium binaphthyldisulfonate as a strong Brønsted acid catalyst. A broad substrate scope was achieved, and the corresponding 3-indolylmethanamines with a chiral quaternary carbon center were obtained in high yields with high enantioselectivities. The addition of a catalytic amount of acetic acid considerably promoted the reaction, and a gram-scale reaction could be achieved with reduced catalyst loading.

DOI： 10.1021/acscatal.7b03708

Application of Detonation Waves to Rocket Engine Chamber

Synthesis of 1,1’-spirobiindane-7,7’-disulfonic acid and disulfonimide: Application for catalytic asymmetric aminalization Reviewed Open Access

Takumaru Kurihara, Shun Satake, Manabu Hatano, Kazuaki Ishihara, Tatsuhiko Yoshino, Shigeki Matsunaga

Chem. Asian J. Vol. 13 ( 17 ) page： 2373 - 2377 2018

Chiral supramolecular U-shaped catalysts induce the multiselective Diels–Alder reaction of propargyl aldehyde Reviewed

Manabu Hatano, Tatsuhiro Sakamoto, Tomokazu Mizuno, Yuta Goto, Kazuaki Ishihara

J. Am. Chem. Soc. Vol. 2018 2018

Chiral pyrophosphoric acid catalysts for the para-selective and enantioselective aza-Friedel–Crafts reaction of phenols Invited Reviewed Open Access

Haruka Okamoto, Kohei Toh, Takuya Mochizuki, Hidefumi Nakatsuji, Akira Sakakura, Manabu Hatano, Kazuaki Ishihara

Synthesis Vol. 50 2018

Bronsted Acid/Lewis Base Hybrid Complexes Invited Reviewed

Hatano Manabu, Ishihara Kazuaki

CHIRAL LEWIS ACIDS Vol. 62 page： 91 - 120 2018

Kasahara, J; Kato, Y; Ishihara, K; Goto, K; Matsuoka, K; Matsuo, A; Funaki, I; Moriai, H; Nakata, D; Higashino, K; Tanatsugu, N

DETONATION CONTROL FOR PROPULSION: PULSE DETONATION AND ROTATING DETONATION ENGINES page： 61 - 76 2018

Selenium-Iodine Cooperative Catalyst for Chlorocyclization of Tryptamine Derivatives Reviewed

Takahiro Horibe, Shuhei Ohmura, Kazuaki Ishihara

ORGANIC LETTERS Vol. 19 ( 20 ) page： 5525 - 5528 2017.10

Language：English Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Chlorocyclization oftryptamine derivatives has been developed with the use of a - diphenyl diselenide-iodine cooperative catalyst. Various tryptamine derivatives can be smoothly converted to the corresponding C3a-chlorohexahydropyrrolo[233-b]indoles. Additionally, we, demonstrate the formAl total syntheses of (-)-psychotriasine and- (-)-acetylardeernin by introducing nucleophiles to the C3a poSition of the products.

DOI： 10.1021/acs.orglett.7b02613

Enantioselective Conjugate Hydrocyanation of alpha,beta-Unsaturated N-Acylpyrroles Catalyzed by Chiral Lithium(I) Phosphoryl Phenoxide Reviewed

Manabu Hatano, Katsuya Yamakawa, Kazuaki Ishihara

ACS CATALYSIS Vol. 7 ( 10 ) page： 6686 - 6690 2017.10

Language：English Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Enantioselective conjugate hydrocyanation of alpha,beta-unsaturated N-acylpyrroles with the combined use of Me3SiCN, LiCN, and HCN has been developed in the presence of a chiral lithium(I) phosphoryl phenoxide catalyst. This reaction is useful for a variety of N-acylpyrroles, including previously unreported substrates, such as heteroaryl and halogen-substituted N-cinnamoylpyrroles. A gram-scale reaction and subsequent transformations to a (R)-succinate, (S)paraconic acid, and (R)-baclofen demonstrate an entry for the practical synthesis of optically active beta-substituted gamma-amino butyric acids (GABA).

DOI： 10.1021/acscatal.7b02551

Design of Boronic Acid-Base Complexes as Reusable Homogeneous Catalysts in Dehydrative Condensations between Carboxylic Acids and Amines Reviewed

Yanhui Lu, Ke Wang, Kazuaki Ishihara

ASIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 6 ( 9 ) page： 1191 - 1194 2017.9

Language：English Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

Two novel boronic acid-base complexes were developed as reusable homogeneous catalysts for amide condensation. First, quaternary ammonium resin-bound boronates were shown to be effective catalysts that might release free boronic acids during reactions and could be regenerated afterwards. Next, a 1:1 mixture of 3,5-dinitro-4-tolueneboronic acid and 4-(N,N-dimethylamino)pyridine N-oxide (DMAPO) or 4-(N,N,-dimethylamino)pyridine (DMAP) cooperatively promoted amide formation and precipitated as an acid-base solid complex after cooling. These inexpensive and reusable complexes may be useful in large-scale process chemistry.

DOI： 10.1002/ajoc.201700194

4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols Reviewed

Enantioselective cycloaddition of styrenes with aldimines catalyzed by a chiral magnesium potassium binaphthyldisulfonate cluster as a chiral Brønsted acid catalyst Reviewed

Manabu Hatano, Keisuke Nishikawa, Kazuaki Ishihara

Journal of the American Chemical Society Vol. 139 ( 25 ) page： 8424-8427 2017.5

Muhammet Uyanik, Tatsuya Mutsuga, Kazuaki Ishihara

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 56 ( 14 ) page： 3956 - 3960 2017.3

Language：English Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

A site-selective hydroxylative dearomatization of 2-substituted phenols to either 1,2-benzoquinols or their cyclodimers, catalyzed by 4,5-dimethyl-2-iodoxybenzenesulfonic acid with Oxone, has been developed. Natural products such as biscarvacrol and lacinileneC methyl ether could be synthesized efficiently under mild reaction conditions. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of phenols. The corresponding 1,2-quinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.

DOI： 10.1002/anie.201612463

Design of High Performance Catalysts Based on Acid-Base Combination Chemistry

Enantioselective synthesis of masked benzoquinones using designer chiral hypervalent organoiodine(III) catalysis Reviewed

Muhammet Uyanik, Niiha Sasakura, Masahiro Mizuno, Kazuaki Ishihara

ACS Catalysis Vol. 7 ( 1 ) page： 872-876 2017.2

Design of High Performance Catalysts Based on Acid-Base Combination Chemistry Invited Reviewed

Kazuaki Ishihara

Vol. 75 ( 2 ) page： 98-110 2017.2

Ishihara Kazuaki

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN Vol. 75 ( 2 ) page： 6 - 18 2017.2

AMMONIUM HYPOIODITE-CATALYZED PEROXIDATIVE DEAROMATIZATION OF PHENOLS Reviewed Open Access

Muhammet Uyanik, Kohei Nishioka, Kazuaki Ishihara

HETEROCYCLES Vol. 95 ( 2 ) page： 1132 - 1147 2017.1

Language：English Publishing type：Research paper (scientific journal) Publisher：PERGAMON-ELSEVIER SCIENCE LTD

Here, we report the first transition metal-free peroxidative dearomatization of phenols using hypoiodite catalysis with TBHP. Hypoiodite salts are generated in situ from the corresponding quaternary ammonium iodides in the presence of TBHP, and the oxidative coupling reaction proceeds efficiently under mild conditions. The dearomatized products are versatile synthetic intermediates for further synthetic transformations to various complex structures including heterocycles. As a demonstration, the further oxidation of the unsaturated peroxide with TBHP afforded the corresponding peroxy epoxide in good yield.

DOI： 10.3987/COM-16-S(S)84