2023/09/23 更新

モリモト ヒロユキ
森本 浩之
MORIMOTO Hiroyuki
Scopus 論文情報  
総論文数: 0  総Citation: 0  h-index: 15

Citation Countは当該年に発表した論文の被引用数

所属
大学院工学研究院 物質工学研究系
職名
准教授
外部リンク

研究キーワード

  • 有機合成化学

研究分野

  • ナノテク・材料 / 有機合成化学

出身学校

  • 2004年03月   東京大学   薬学部   薬学科   卒業   日本国

取得学位

  • 東京大学  -  博士(薬学)   2009年03月

  • 東京大学  -  修士(薬学)   2006年03月

学内職務経歴

  • 2023年04月 - 現在   九州工業大学   大学院工学研究院   物質工学研究系     准教授

所属学会・委員会

論文

  • Functional Group Evaluation Kit for Digitalization of Information on the Functional Group Compatibility and Chemoselectivity of Organic Reactions 査読有り 国際誌

    Saito Natsuki, Nawachi Anna, Kondo Yuta, Choi Jeesoo, Morimoto Hiroyuki, Ohshima Takashi

    Bulletin of the Chemical Society of Japan ( 公益社団法人 日本化学会 )   96 ( 5 )   465 - 474   2023年05月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    <p>Digitalization of information on organic reactions is essential for developing next-generation organic syntheses with artificial intelligence and machine-learning (ML) methods. In this regard, reliable information on functional group compatibility and chemoselectivity is critical for understanding the applicability of the reactions. Herein, we report the digitalization of organic reactions using a functional group evaluation (FGE) kit that allows for accurate and rapid assessment of information on the functional group compatibility and chemoselectivity of given organic reactions. Our 26 FGE compounds were used to evaluate 4 types of organic reactions (i.e., cross-coupling, proline-catalyzed aldol, condensation, and ketimine synthesis reactions). As a result, we obtained valuable information for developing a new model of retrosynthetic analysis tools and a deeper understanding of these reactions.</p>

    DOI: 10.1246/bcsj.20230047

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  • Organocatalytic Direct Enantioselective Hydrophosphonylation of N-Unsubstituted Ketimines for the Synthesis of α-Aminophosphonates 査読有り 国際誌

    Yamada K., Kondo Y., Kitamura A., Kadota T., Morimoto H., Ohshima T.

    ACS Catalysis   13 ( 5 )   3158 - 3163   2023年03月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    We report an organocatalyzed direct enantioselective hydrophosphonylation of N-unsubstituted ketimines that affords N-unprotected α-tetrasubstituted α-aminophosphonates without protection/deprotection steps. The reaction is suitable for N-unsubstituted isatin-derived and trifluoromethyl ketimines, affording products in high yields with excellent enantioselectivity. Applications of the reaction and a proposed transition state model are also described.

    DOI: 10.1021/acscatal.2c05953

    Scopus

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  • Catalytic Enantioselective Strecker Reaction of Isatin-Derived N-Unsubstituted Ketimines 査読有り 国際誌

    Kadota T., Sawa M., Kondo Y., Morimoto H., Ohshima T.

    Organic Letters ( American Chemical Society )   23 ( 12 )   4553 - 4558   2021年06月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    A catalytic enantioselective Strecker reaction of isatin-derived N-unsubstituted ketimines directly afforded the N-unprotected α-aminonitriles with a tetrasubstituted carbon stereocenter in up to 99% ee without requiring protection/deprotection steps. One-pot Strecker reactions from the parent carbonyl compounds were also realized with comparable yields and enantioselectivities. Direct transformations of the N-unprotected α-aminonitrile products streamlined the synthesis of unnatural amino acid derivatives and achieved the shortest one-pot stereoselective routes to a biologically active compound reported to date.

    DOI: 10.1021/acs.orglett.1c01194

    Scopus

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  • Recent Progress on Catalytic Addition Reactions to N-Unsubstituted Imines 査読有り 国際誌

    Morisaki K., Morimoto H., Ohshima T.

    ACS Catalysis   10 ( 12 )   6924 - 6951   2020年06月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Catalytic addition reactions to N-unsubstituted (N-unprotected) imines can provide a more straightforward synthesis of amines. This direct process eliminates the unnecessary protecting-group manipulations that are required with N-substituted (N-protected) imines and can contribute to the development of green chemistry. Although their use has been limited due to difficulties associated with the nature of N-unsubstituted imines, recently developed catalytic methods enable the use of N-unsubstituted imines as electrophiles in various catalytic addition reactions. To facilitate an understanding of the state of the art development of synthetic methodologies, herein we review recent progress on catalytic addition reactions to N-unsubstituted imines. We begin with an overview of the chemistry of N-unsubstituted imines, followed by a summary of recent progress categorized according to the reaction type. We hope this review will help to stimulate further development of greener syntheses of nitrogen-containing compounds.

    DOI: 10.1021/acscatal.0c01212

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  • Direct Catalytic Alcoholysis of Unactivated 8-Aminoquinoline Amides 査読有り 国際誌

    Deguchi T., Xin H.L., Morimoto H., Ohshima T.

    ACS Catalysis   7 ( 5 )   3157 - 3161   2017年05月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Direct catalytic alcoholysis of unactivated amides is one of the most difficult challenges in organic chemistry, and an applicable method for cleaving amides used as directing groups in regioselective functionalization reactions has not been reported. Herein, we report direct catalytic alcoholysis of 8-aminoquinoline amides, which are highly effective directing groups in regioselective functionalization reactions. The reactions proceeded with a simple combination of substrates, air-stable catalysts, and alcohols, affording the corresponding esters in good yields with broad functional group tolerance. Highly chemoselective cleavage of the 8-aminoquinoline amides in the presence of related carbonyl functionalities and preliminary mechanistic studies are also described.

    DOI: 10.1021/acscatal.7b00442

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  • Visible-Light-Induced Aminochlorination of Alkenes 査読有り 国際誌

    Mejri E., Higashida K., Kondo Y., Nawachi A., Morimoto H., Ohshima T., Sawamura M., Shimizu Y.

    Organic Letters   25 ( 24 )   4581 - 4585   2023年06月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Photoinduced N-internal vicinal aminochlorination of styrene-type terminal alkenes was developed. The reaction proceeded without any catalyst, and the use of N-chloro(fluorenone imine) as both a photoactivatable aminating agent and a chlorinating agent was essential. The imine moiety, introduced at the internal position of the alkenes, could be hydrolyzed under mild conditions to provide versatile β-chlorinated primary amines, the synthetic utility of which was demonstrated by several transformations.

    DOI: 10.1021/acs.orglett.3c01645

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  • O- and N-Selective Electrophilic Activation of Allylic Alcohols and Amines in Pd-Catalyzed Direct Alkylation 査読有り 国際誌

    Lin L., Kataoka S., Hirayama K., Shibuya R., Watanabe K., Morimoto H., Ohshima T.

    Chemical &amp; pharmaceutical bulletin ( 公益社団法人 日本薬学会 )   71 ( 2 )   101 - 106   2023年01月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Catalytic control of chemoselectivity is crucial in the synthesis of highly functionalized compounds. Although there are reports of efficient chemoselective reactions of alcohols and amines as nucleophiles, there are no reports of the chemoselective activation of alcohols and amines as electrophiles. In this study, highly O- and N-selective electrophilic activation of allylic alcohols and amines was achieved in Pd-catalyzed direct allylic alkylation. Allylamines were inherently more reactive than allylic alcohols (N-selectivity). On the other hand, the addition of catalytic amounts of 9-phenanthreneboronic acid preferentially activated allylic alcohols over allylamines (O-selectivity). Density functional theory (DFT) calculations suggested that the N-selectivity is due to the selective activation of allylic amines with ammonium cations, and boronate formation accelerates the activation of allylic alcohols.

    DOI: 10.1248/cpb.c22-00745

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    CiNii Research

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  • One-Pot Catalytic Synthesis of α-Tetrasubstituted Amino Acid Derivatives via in Situ Generation of N-Unsubstituted Ketimines 査読有り 国際誌

    Kondo Y., Hirazawa Y., Kadota T., Yamada K., Morisaki K., Morimoto H., Ohshima T.

    Organic Letters   24 ( 36 )   6594 - 6598   2022年09月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    A one-pot catalytic synthesis of α-tetrasubstituted amino acid derivatives via in situ generation of N-unsubstituted ketimines is reported. Because of the irreversible formation of N-unsubstituted ketimines, the yields were higher than those generated under the conventional one-pot reaction conditions. This process prevents the need to isolate unstable N-unsubstituted ketimines with alkyl substituents and streamlines the synthesis of highly congested α-amino acid derivatives.

    DOI: 10.1021/acs.orglett.2c02587

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  • A TRPC3/6 Channel Inhibitor Promotes Arteriogenesis after Hind‐Limb Ischemia 査読有り 国際誌

    Shimauchi T., Numaga‐tomita T., Kato Y., Morimoto H., Sakata K., Matsukane R., Nishimura A., Nishiyama K., Shibuta A., Horiuchi Y., Kurose H., Kim S.G., Urano Y., Ohshima T., Nishida M.

    Cells   11 ( 13 )   2022年07月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Retarded revascularization after progressive occlusion of large conductance arteries is a major cause of bad prognosis for peripheral artery disease (PAD). However, pharmacological treatment for PAD is still limited. We previously reported that suppression of transient receptor potential canonical (TRPC) 6 channel activity in vascular smooth muscle cells (VSMCs) facilitates VSMC differentiation without affecting proliferation and migration. In this study, we found that 1−benzilpiperadine derivative (1−BP), a selective inhibitor for TRPC3 and TRPC6 channel activities, induced VSMC differentiation. 1‐ BP‐treated mice showed increased capillary arterialization and improvement of peripheral circulation and skeletal muscle mass after hind‐limb ischemia (HLI) in mice. 1−BP had no additive effect on the facilitation of blood flow recovery after HLI in TRPC6−deficient mice, suggesting that suppression of TRPC6 underlies facilitation of the blood flow recovery by 1−BP. 1−BP also improved vascular nitric oxide bioavailability and blood flow recovery after HLI in hypercholesterolemic mice with endothelial dysfunction, suggesting the retrograde interaction from VSMCs to endothelium. These results suggest that 1−BP becomes a potential seed for PAD treatments that target vascular TRPC6 channels.

    DOI: 10.3390/cells11132041

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  • 無保護ケチミンを活用した環境調和型新規触媒的含窒素化合物合成手法の開発 招待有り 査読有り

    森本 浩之

    有機合成化学協会誌 ( 公益社団法人 有機合成化学協会 )   80 ( 1 )   2 - 13   2022年01月

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    担当区分:筆頭著者, 最終著者, 責任著者   記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)

    <p>Herein we report our recent efforts on the greener catalytic synthetic methods of nitrogen-containing compounds using <i>N</i>-unprotected ketimines. We found that alkynylation of <i>N</i>-unprotected trifluoromethyl ketimines proceeded in the presence of zinc catalysts, providing the products in good yield with broad functional group tolerance and unique chemoselectivity. Next, we extended the methodology to catalytic stereoselective addition reactions and found that a direct Mannich-type reaction, a Friedel-Crafts-type alkylation reaction, a decarboxylative Mannich-type reaction, and an arylation reaction proceeded in the presence of appropriate metal or organocatalysts to give α-tetrasubstituted amines in high yield and stereoselectivity. The detailed scope and some mechanistic insights of these reactions are also presented.</p>

    DOI: 10.5059/yukigoseikyokaishi.80.2

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    CiNii Article

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    その他リンク: https://www.jstage.jst.go.jp/article/yukigoseikyokaishi/80/1/80_2/_pdf

  • Development and Integration of New Green Reactions 国際誌

    大嶋 孝志, 森本 浩之

    Middle Molecular Strategy   15   275 - 295   2021年01月

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    記述言語:英語   掲載種別:記事・総説・解説・論説等(学術雑誌)

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  • C-C Bond Cleavage of Unactivated 2-Acylimidazoles 査読有り 国際誌

    Xin H.L., Pang B., Choi J., Akkad W., Morimoto H., Ohshima T.

    Journal of Organic Chemistry   85 ( 18 )   11592 - 11606   2020年09月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    2-Acylimidazoles are widely used as post-Transformable carboxylic acid equivalents in chemoselective and enantioselective reactions. Their transformations, however, require pretreatment with highly reactive, toxic methylating reagents to facilitate C-C bond cleavage. Here, we demonstrate that such pretreatment can be avoided and the C-C bond cleaved under neutral conditions without the use of additional reagents or catalysts. The scope of the reaction, including the use of products reported in the literature as substrates, and some mechanistic insights are described.

    DOI: 10.1021/acs.joc.0c01458

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  • Recent progress towards the use of benzophenone imines as an ammonia equivalent 査読有り 国際誌

    Kondo Y., Morimoto H., Ohshima T.

    Chemistry Letters ( 公益社団法人 日本化学会 )   49 ( 5 )   497 - 504   2020年05月

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    担当区分:責任著者   記述言語:英語   掲載種別:記事・総説・解説・論説等(学術雑誌)

    Benzophenone imine and its derivatives are useful ammonia equivalents for synthesizing primary amines, readily achieving the selective formation of primary amines and obtaining easily deprotectable imines as the product. These advantages have led to the development of various CN bond-forming reactions in recent years. In this Highlight Review, we summarize the progress related to their reaction patterns.

    DOI: 10.1246/cl.200099

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  • Rhodium(I)/Chiral Diene-Catalyzed Enantioselective Addition of Boronic Acids to N-Unsubstituted Isatin-Derived Ketimines 査読有り 国際誌

    Yonesaki R., Kusagawa I., Morimoto H., Hayashi T., Ohshima T.

    Chemistry - An Asian Journal   15 ( 4 )   499 - 502   2020年02月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Enantioselective addition of boronic acids to N-unsubstituted isatin-derived ketimines was realized using rhodium(I)/chiral diene catalysts. The reactions can be performed in the presence of catalytic amounts of a base to give adducts in high yield with high enantioselectivity. Preliminary mechanistic information including a computational model to explain the observed enantioselectivity is also provided.

    DOI: 10.1002/asia.201901745

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  • Scandium(III) Triflate Catalyzed Direct Synthesis of N-Unprotected Ketimines 査読有り 国際誌

    Kondo Y., Kadota T., Hirazawa Y., Morisaki K., Morimoto H., Ohshima T.

    Organic Letters   22 ( 1 )   120 - 125   2020年01月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    N-Unprotected ketimines are useful substrates and intermediates for synthesizing valuable nitrogen-containing compounds, but their potential applicability is limited by the available synthetic methods. To address this issue, we report a scandium(III) triflate catalyzed direct synthesis of N-unprotected ketimines. Using commercially available reagents and Lewis acid catalysts, ketones were directly transformed into the corresponding N-unprotected ketimines in high yields with broad functional group tolerance, even in multigram scales. The reactions were readily applicable for one-pot synthesis of important compounds such as a glycine Schiff base without isolation of N-unprotected ketimine intermediates. Preliminary mechanistic studies to clarify the reaction mechanism are also described.

    DOI: 10.1021/acs.orglett.9b04038

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  • Mechanistic studies of nickel(II)-catalyzed direct alcoholysis of 8-aminoquinoline amides 査読有り 国際誌

    Morimoto H., Akkad W., Deguchi T., Ohshima T.

    Heterocycles   101 ( 2 )   471 - 485   2020年01月

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    担当区分:筆頭著者, 責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    This paper describes the mechanistic aspects of nickel(II)-catalyzed direct alcoholysis of 8-aminoquinoline amides. Kinetic experiments suggested that the nickel(II) catalyst existed in an oligomeric form in the resting state, and the 8-aminoquinoline generated after cleavage coordinated to the nickel(II) catalyst to decelerate the reaction. In addition, density functional theory calculations revealed that the reactions proceeded via the intermediate with N,N,O-tridentate coordination of 8-aminoquinoline amides to the nickel(II) metal center, and that the alcoholysis reaction did not involve deprotonation of the N-H bond of 8-aminoquinoline amides, in contrast to the proposed mechanism for C-H bond functionalization reactions of 8-aminoquinoline amides.

    DOI: 10.3987/COM-19-S(F)30

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  • Identification of candidate molecular targets of the novel antineoplastic antimitotic NP-10 査読有り 国際誌

    Yokoyama T., Yukuhiro M., Iwasaki Y., Tanaka C., Sankoda K., Fujiwara R., Shibuta A., Higashi T., Motoyama K., Arima H., Yoshida K., Sugimoto N., Morimoto H., Kosako H., Ohshima T., Fujita M.

    Scientific Reports   9 ( 1 )   2019年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    We previously reported the identification of a novel antimitotic agent with carbazole and benzohydrazide structures: N′-[(9-ethyl-9H-carbazol-3-yl)methylene]-2-iodobenzohydrazide (code number NP-10). However, the mechanism(s) underlying the cancer cell-selective inhibition of mitotic progression by NP-10 remains unclear. Here, we identified NP-10-interacting proteins by affinity purification from HeLa cell lysates using NP-10-immobilized beads followed by mass spectrometry. The results showed that several mitosis-associated factors specifically bind to active NP-10, but not to an inactive NP-10 derivative. Among them, NUP155 and importin β may be involved in NP-10-mediated mitotic arrest. Because NP-10 did not show antitumor activity in vivo in a previous study, we synthesized 19 NP-10 derivatives to identify more effective NP-10-related compounds. HMI83-2, an NP-10-related compound with a Cl moiety, inhibited HCT116 cell tumor formation in nude mice without significant loss of body weight, suggesting that HMI83-2 is a promising lead compound for the development of novel antimitotic agents.

    DOI: 10.1038/s41598-019-53259-2

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  • A Convenient Preparation Method for Benzophenone Imine Catalyzed by Tetrabutylammonium Fluoride 査読有り 国際誌

    Kondo Y., Morisaki K., Hirazawa Y., Morimoto H., Ohshima T.

    Organic Process Research and Development   23 ( 8 )   1718 - 1724   2019年08月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Benzophenone imine is a useful ammonia equivalent in the Buchwald-Hartwig amination and an important intermediate for the synthesis of N-protected primary amines. However, the conventional synthesis of benzophenone imine requires stoichiometric amounts of metal reagents or high-pressure conditions. Herein we report a facile method for preparing benzophenone imine to enhance its potential utility. The reaction is performed by mixing commercially available benzophenone and bis(trimethylsilyl)amine in the presence of a catalytic amount of tetrabutylammonium fluoride at ambient temperature and pressure and can be readily applied to a multigram-scale synthesis even in a standard academic laboratory setup. Preliminary mechanistic studies and the application of the reaction to one-pot benzophenone imine synthesis/Buchwald-Hartwig amination are also reported.

    DOI: 10.1021/acs.oprd.9b00226

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  • Ammonium Salt-Accelerated Hydrazinolysis of Unactivated Amides: Mechanistic Investigation and Application to a Microwave Flow Process 査読有り 国際誌

    Noshita M., Shimizu Y., Morimoto H., Akai S., Hamashima Y., Ohneda N., Odajima H., Ohshima T.

    Organic Process Research and Development   23 ( 4 )   588 - 594   2019年04月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    A study of ammonium salt-accelerated hydrazinolysis of unactivated amides is described. We first studied the reaction mechanism by kinetic experiments and DFT calculations and found that cooperation of the hydrazinium salt and hydrazine is important for promoting the cleavage of unactivated amides. Next, we applied the reaction to a microwave flow process, and the amine products were isolated on a multigram scale.

    DOI: 10.1021/acs.oprd.8b00424

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  • 窒素上無保護ケチミンに対する触媒的不斉求核付加反応の開発――四置換炭素含有アミノ酸の環境調和型新規合成手法への展開 招待有り 査読有り

    森本 浩之

    化学と工業   72   780 - 781   2019年01月

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    担当区分:筆頭著者, 最終著者, 責任著者   記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)

    CiNii Research

  • 有機触媒による窒素上無保護α-ケチミノエステルに対する直接的不斉求核付加反応の開発 招待有り 査読有り

    森本 浩之

    化学工業(化学工業社)   70   668 - 672   2019年01月

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    担当区分:筆頭著者, 責任著者   記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)

    CiNii Research

  • 3-Mono-Substituted BINOL Phosphoric Acids as Effective Organocatalysts in Direct Enantioselective Friedel–Crafts-Type Alkylation of N-Unprotected α-Ketiminoester 査読有り 国際誌

    Yonesaki R., Kondo Y., Akkad W., Sawa M., Morisaki K., Morimoto H., Ohshima T.

    Chemistry - A European Journal   24 ( 57 )   15211 - 15214   2018年10月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Although BINOL-derived phosphoric acids are among the most widely used chiral Brønsted acid organocatalysts, their structures are mostly limited to 3,3′-disubstituted ones and simple 3-mono-substituted ones without any polar functionalities on the 3-substituent have not been used in highly enantioselective reactions. This work reports such 3-mono-substituted analogues as effective organocatalysts in direct highly enantioselective Friedel–Crafts-type alkylation of N-unprotected α-ketiminoester. The origin of the observed high enantioselectivity with the 3-mono-substituted catalyst is also discussed.

    DOI: 10.1002/chem.201804078

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  • Catalytic Enantioselective Decarboxylative Mannich-Type Reaction of N-Unprotected Isatin-Derived Ketimines 査読有り 国際誌

    Sawa M., Miyazaki S., Yonesaki R., Morimoto H., Ohshima T.

    Organic Letters   20 ( 17 )   5393 - 5397   2018年09月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    The first catalytic enantioselective decarboxylative Mannich-type reaction of N-unprotected ketimines is reported, directly providing N-unprotected 3-tetrasubstituted 3-aminooxindoles in high yield and ee without protection/deprotection steps. The utility of this reaction is demonstrated in the short step synthesis of (+)-AG-041R.

    DOI: 10.1021/acs.orglett.8b02306

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  • Development of direct enantioselective alkynylation of αketoester and α-ketiminoesters catalyzed by phenylbis(oxazoline)Rh(III) complexes 査読有り

    Morisaki K., Morimoto H., Mashima K., Ohshima T.

    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry ( 公益社団法人 有機合成化学協会 )   76 ( 3 )   226 - 240   2018年01月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Direct catalytic enantioselective alkynylation of carbonyl compounds and imines is one of the most efficient approaches for the synthesis of propargylic alcohols and propargylamines, which are potent building blocks for synthesizing functionalized molecules. While a variety of methods for the reactions with aldehydes and aldimines have been established, the reactions with ketones and ketimines remain underdeveloped due to their reduced reactivity and difficulty in stereocontrol. In this account, we summarized our studies on direct enantioselective alkynylation reaction of α-ketoester and α-ketiminoesters catalyzed by phenylbis(oxazolinephebox)-rhodium(III) complexes, affording enantioenriched propargyl alcohols and propargylamines with a tetrasubsti-tuted carbon stereocenter under proton-transfer conditions. The catalytic system was compatible to a wide range of functional groups, including electrophilic formyl groups, and allowed for the development of an efficient method to access enantioenriched α-CF3-substituted thalidomide analogs. Mechanistic studies revealed that generation of the (alkynyl(phebox)Rh(III) complex from the (diacetatophebox)Rh(III) complex determined the overall reaction rate in the initial stages of the reaction. These results, along with the observed facile exchange of the alkynyl ligand on the (alkynylphebox)Rh(III) complexes, led us to use (trimethylsilylethynylphebox)Rh(III) complexes as a new pre-catalyst. The new catalytic system with (trimethylsilylethynylphebox)Rh (III) precatalysts exhibited enhanced catalytic performance, reduced catalyst loading to as low as 0.5 mol%, and expanded the substrate scope of the reaction with less reactive α-ketiminophos-phonate and cyclic N-sulfonyl α-ketiminoesters.

    DOI: 10.5059/yukigoseikyokaishi.76.226

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    CiNii Article

    CiNii Research

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  • Direct Access to N-Unprotected α- and/or β-Tetrasubstituted Amino Acid Esters via Direct Catalytic Mannich-Type Reactions Using N-Unprotected Trifluoromethyl Ketimines 査読有り 国際誌

    Sawa M., Morisaki K., Kondo Y., Morimoto H., Ohshima T.

    Chemistry - A European Journal   23 ( 67 )   17022 - 17028   2017年12月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Direct catalytic C−C bond-forming addition to N-unprotected ketimines is an efficient and straightforward method of synthesizing N-unprotected tetrasubstituted amines that eliminates prior protection/deprotection steps and allows facile transformation of the products. Despite its advantages, however, N-unprotected ketimines have difficulties in C−C bond-forming reactions, and only a limited number of reactions and substrates are reported compared with their N-protected counterparts. Herein we report that N-unprotected trifluoromethyl ketimines are effective for C−C bond-forming reactions using Mannich-type reactions as a model case. We demonstrate that Lewis acid catalysis was effective for promoting reactions with various N-unprotected trifluoromethyl ketimines, and thiourea organocatalysis was effective for promoting highly enantioselective reactions with various carbonyl nucleophiles, providing direct access to various N-unprotected α- and/or β-tetrasubstituted amino acid esters. Furthermore, direct construction of vicinal tetrasubstituted chiral carbon stereocenters was achieved for the first time in a highly enantio- and diastereoselective manner. These results demonstrate the potential of N-unprotected ketimines as substrates applicable to many other addition reactions.

    DOI: 10.1002/chem.201703516

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  • Boronic Acid Accelerated Three-Component Reaction for the Synthesis of α-Sulfanyl-Substituted Indole-3-acetic Acids 査読有り

    Das A., Watanabe K., Morimoto H., Ohshima T.

    Organic Letters   19 ( 21 )   5794 - 5797   2017年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Boronic acid was used to accelerate a three-component reaction of indoles, thiols, and glyoxylic acids for the synthesis of α-sulfanyl-substituted indole-3-acetic acids. Boronic acid catalysis to activate the α-hydroxy group in α-hydroxycarboxylic acid intermediates and intramolecular assistance by free carboxylic acid were the keys to accelerating the product formation.

    DOI: 10.1021/acs.orglett.7b02727

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  • Synthesis of 1-tetrasubstituted 2,2,2-trifluoroethylamine derivatives via palladium-catalyzed allylation of sp<sup>3</sup> C–H bonds 査読有り 国際誌

    Morisaki K., Kondo Y., Sawa M., Morimoto H., Ohshima T.

    Chemical and Pharmaceutical Bulletin ( 公益社団法人 日本薬学会 )   65 ( 11 )   1089 - 1092   2017年01月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    This note describes the construction of tetrasubstituted carbon stereocenters via palladium-catalyzed allylation of sp3 C–H bonds of 2,2,2-trifluoroethylamine derivatives. The presence of 2-pyridyl group of the imines derived from 1-substituted-2,2,2-trifluoroethylamine was key to promoting the reaction efficiently, allowing an access to a variety of 1-allylated 2,2,2-trifluoroethylamine derivatives with tetrasubstituted carbon stereocenters.

    DOI: 10.1248/cpb.c17-00580

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    CiNii Article

    CiNii Research

    PubMed

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  • Direct enantioselective alkynylation of α-ketoesters and α-ketiminoesters catalyzed by [bis(oxazoline)phenyl]rhodium(III) complexes 査読有り 国際誌

    Morisaki K., Morimoto H., Mashima K., Ohshima T.

    Heterocycles   95 ( 2 )   637 - 661   2017年01月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    This review summarizes our studies of the direct enantioselective alkynylation of α-ketoesters and α-ketiminoesters catalyzed by [bis(oxazoline)phenyl]rhodium(III) ((phebox)Rh(III)) complexes. The reactions provide chiral α-tetrasubstituted propargyl alcohols and propargylamines under proton-transfer conditions in high yield and with high enantioselectivity. The unique nature of (phebox)Rh(III) complexes allows the reactions to occur in the presence of various functional groups, including an electrophilic aldehyde functionality. Mechanistic studies revealed that the generation of (alkynyl)Rh(III) complexes limited the overall reactivity, which led us to use (trimethylsilylethynyl)(phebox)Rh(III) complexes as efficient pre-catalysts. The use of (trimethylsilylethynyl)(phebox)Rh(III) complexes reduced catalyst loading to as low as 0.5 mol%, and expanded the substrate scope to unprecedented α-ketiminophosphonate and cyclic N-sulfonyl α-ketiminoesters.

    DOI: 10.3987/REV-16-SR(S)4

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  • Direct access to: N -unprotected tetrasubstituted propargylamines via direct catalytic alkynylation of N -unprotected trifluoromethyl ketimines 査読有り 国際誌

    Morisaki K., Morimoto H., Ohshima T.

    Chemical Communications   53 ( 47 )   6319 - 6322   2017年01月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Direct catalytic alkynylation of N-unprotected trifluoromethyl ketimines is reported for the first time. A combination of catalytic amounts of diethylzinc and carboxylic acids promoted the reactions under proton-transfer conditions, allowing an unprecedented direct access to N-unprotected α-tetrasubstituted primary amines without additional deprotection steps.

    DOI: 10.1039/c7cc02194a

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  • Diethylenetriamine-Mediated Direct Cleavage of Unactivated Carbamates and Ureas 査読有り 国際誌

    Noshita M., Shimizu Y., Morimoto H., Ohshima T.

    Organic Letters   18 ( 23 )   6062 - 6065   2016年12月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Diethylenetriamine is effective for the direct cleavage of unactivated carbamates and ureas without additional reagents and catalysts. Various carbamates and ureas were cleaved to afford products in good yield, and the reactions were not affected by air or moisture. Unique chemoselective cleavage of carbamate and urea in the presence of amides was also achieved.

    DOI: 10.1021/acs.orglett.6b03016

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  • Mechanistic Studies and Expansion of the Substrate Scope of Direct Enantioselective Alkynylation of α-Ketiminoesters Catalyzed by Adaptable (Phebox)Rhodium(III) Complexes 査読有り 国際誌

    Morisaki K., Sawa M., Yonesaki R., Morimoto H., Mashima K., Ohshima T.

    Journal of the American Chemical Society   138 ( 19 )   6194 - 6203   2016年05月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Mechanistic studies and expansion of the substrate scope of direct enantioselective alkynylation of α-ketiminoesters catalyzed by adaptable (phebox)rhodium(III) complexes are described. The mechanistic studies revealed that less acidic alkyne rather than more acidic acetic acid acted as a proton source in the catalytic cycle, and the generation of more active (acetato-κ2O,O′)(alkynyl)(phebox)rhodium(III) complexes from the starting (diacetato)rhodium(III) complexes limited the overall reactivity of the reaction. These findings, as well as facile exchange of the alkynyl ligand on the (alkynyl)rhodium(III) complexes led us to use (acetato-κ2O,O′)(trimethylsilylethynyl)(phebox)rhodium(III) complexes as a general precatalyst for various (alkynyl)rhodium(III) complexes. Use of the (trimethylsilylethynyl)rhodium(III) complexes as precatalysts enhanced the catalytic performance of the reactions with an α-ketiminoester derived from ethyl trifluoropyruvate at a catalyst loading as low as 0.5 mol % and expanded the substrate scope to unprecedented α-ketiminophosphonate and cyclic N-sulfonyl α-ketiminoesters.

    DOI: 10.1021/jacs.6b01590

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  • A novel anti-microtubule agent with carbazole and benzohydrazide structures suppresses tumor cell growth in vivo 査読有り 国際誌

    Ohira M., Iwasaki Y., Tanaka C., Kuroki M., Matsuo N., Kitamura T., Yukuhiro M., Morimoto H., Pang N., Liu B., Kiyono T., Amemiya M., Tanaka K., Yoshida K., Sugimoto N., Ohshima T., Fujita M.

    Biochimica et Biophysica Acta - General Subjects   1850 ( 9 )   1676 - 1684   2015年05月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Background The mitotic spindles are among the most successful targets of anti-cancer chemotherapy, and they still hold promise as targets for novel drugs. The anti-mitotic drugs in current clinical use, including taxanes, epothilones, vinca alkaloids, and halichondrins, are all microtubule-targeting agents. Although these drugs are effective for cancer chemotherapy, they have some critical problems; e.g., neurotoxicity caused by damage to neuronal microtubules, as well as innate or acquired drug resistance. To overcome these problems, a great deal of effort has been expended on development of novel anti-mitotics. Methods We identified novel microtubule-targeting agents with carbazole and benzohydrazide structures: N′-[(9-ethyl-9H-carbazol-3-yl)methylene]-2-methylbenzohydrazide (code number HND-007) and its related compounds. We investigated their activities against cancer cells using various methods including cell growth assay, immunofluorescence analysis, cell cycle analysis, tubulin polymerization assay, and tumor inhibition assay in nude mice. Results HND-007 inhibits tubulin polymerization in vitro and blocks microtubule formation and centrosome separation in cancer cells. Consequently, it suppresses the growth of various cancer cell lines, with IC<inf>50</inf> values in the range 1.3-4.6 μM. In addition, HND-007 can inhibit the growth of taxane-resistant cancer cells that overexpress P-glycoprotein. Finally, HND-007 can inhibit HeLa cell tumor growth in nude mice. Conclusions and general significance Taken together, these findings suggest that HND-007 is a promising lead compound for development of novel anti-mitotic, anti-microtubule chemotherapeutic agents.

    DOI: 10.1016/j.bbagen.2015.04.013

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  • Direct catalytic anti-Markovnikov addition reactions of oxygen nucleophiles to simple Alkenes 査読有り

    Morimoto H.

    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry   72 ( 12 )   1402 - 1403   2014年12月

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    担当区分:筆頭著者, 最終著者, 責任著者   記述言語:英語   掲載種別:記事・総説・解説・論説等(学術雑誌)

    Development of direct catalytic anti-Markovnikov addition reactions of oxygen nucleophiles to simple alkenes is a difficult challenge due to the propensity to form Markovnikov adducts under ordinary reaction conditions. Herein selected recent examples that realize these reactions with high anti-Markovnikov selectivity are summarized.

    DOI: 10.5059/yukigoseikyokaishi.72.1402

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  • A short scalable route to (-)-α-kainic acid using Pt-catalyzed direct allylic amination 査読有り 国際誌

    Zhang M., Watanabe K., Tsukamoto M., Shibuya R., Morimoto H., Ohshima T.

    Chemistry - A European Journal   21 ( 10 )   3937 - 3941   2014年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    An increased supply of scarce or inaccessible natural products is essential for the development of more sophisticated pharmaceutical agents and biological tools, and thus the development of atom-economical, step-economical and scalable processes to access these natural products is in high demand. Herein we report the development of a short, scalable total synthesis of (-)-α-kainic acid, a useful compound in neuropharmacology that is, however, limited in supply from natural resources. The synthesis features sequential platinum-catalyzed direct allylic aminations and thermal ene-cyclization, enabling the gram-scale synthesis of (-)-α-kainic acid in six steps and 34% overall yield.

    DOI: 10.1002/chem.201406557

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  • Cleavage of unactivated amide bonds by ammonium salt-accelerated hydrazinolysis 査読有り 国際誌

    Shimizu Y., Noshita M., Mukai Y., Morimoto H., Ohshima T.

    Chemical Communications   50 ( 84 )   12623 - 12625   2014年09月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Hydrazinolysis of unactivated amide bonds is significantly accelerated by the addition of ammonium salts. The reactions proceed at 50–70 °C to give amines with broad substrate scope that outperforms existing amide bond cleavage reactions. Application to peptide and amino sugar derivatives is also demonstrated. © Partner Organisations 2014.

    DOI: 10.1039/c4cc02014f

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  • Lanthanum(III) triflate catalyzed direct amidation of esters 査読有り 国際誌

    Morimoto H., Fujiwara R., Shimizu Y., Morisaki K., Ohshima T.

    Organic Letters   16 ( 7 )   2018 - 2021   2014年04月

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    担当区分:責任著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Lanthanum trifluoromethanesulfonate is an effective single-component catalyst for synthesizing a variety of amides directly from esters and amines under mild conditions. Highly selective amidation of esters and amines, as well as catalyst-controlled amidation of esters, demonstrated the effectiveness of the catalyst system. © 2014 American Chemical Society.

    DOI: 10.1021/ol500593v

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  • Rh-catalyzed direct enantioselective alkynylation of α-ketiminoesters 査読有り 国際誌

    Morisaki K., Sawa M., Nomaguchi J.Y., Morimoto H., Takeuchi Y., Mashima K., Ohshima T.

    Chemistry - A European Journal   19 ( 26 )   8417 - 8420   2013年06月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    A green way to amino acids: α-Tetrasubstituted α-amino acid derivatives are formed in high yield and enantioselectivity by using a Rh-catalyzed enantioselective alkynylation of α-ketiminoesters. This reaction, which involves a proton transfer and can be conducted at room temperature, has high substrate scope (see scheme; Cbz=benzyloxycarbonyl, Fmoc=9-fluorenylmethyloxycarbonyl). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/chem.201301237

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  • Microwave-assisted deacylation of unactivated amides using ammonium-salt-accelerated transamidation 査読有り 国際誌

    Shimizu Y., Morimoto H., Zhang M., Ohshima T.

    Angewandte Chemie - International Edition   51 ( 34 )   8564 - 8567   2012年08月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Easy does it! The chemoselective oxidative ?-C(sp3)H alkylation/cyclization reaction of N-benzyl carbamates using simple mono-, di-, and trisubstituted olefins provides functionalized N-heterocycles such as oxazinones (see picture). A TEMPO oxoammonium salt serves as the oxidant, making it possible to carry out the reaction at low temperatures. Neither a metal catalyst nor preactivation in the ?-position to the nitrogen group are needed.

    DOI: 10.1002/anie.201202354

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  • Stereodivergent direct catalytic asymmetric mannich-type reactions of α-isothiocyanato ester with ketimines 査読有り 国際誌

    Lu G., Yoshino T., Morimoto H., Matsunaga S., Shibasaki M.

    Angewandte Chemie - International Edition   50 ( 19 )   4382 - 4385   2011年05月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Now accessible: Sterically hindered vicinal tetrasubstituted carbon stereocenters, which are not accessible by asymmetric hydrogenation, were constructed by a catalytic asymmetric C-C bond formation (see scheme; Dpp=diphenylphosphinoyl). By changing the Group 2 metal center, stereodivergent access to α,β-tetrasubstituted α,β-diamino esters was realized. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/anie.201101034

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  • A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides 査読有り 国際誌

    Morimoto H., Tsubogo T., Litvinas N., Hartwig J.

    Angewandte Chemie - International Edition   50 ( 16 )   3793 - 3798   2011年04月

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    担当区分:筆頭著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    (Chemical Presented) Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides and some aryl bromides with trifluoromethyl and perfluoroalkylcopper(I) phenanthroline complexes occur with broad scope at 25-50 8C (see scheme). The trifluoromethyl complex is prepared from inexpensive reagents and can be used in situ or isolated. The reactions tolerate a range of substituents and also occur with heteroaromatic systems. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.201100633

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  • Catalytic asymmetricaza-Morita-Baylis-Hillman reaction of methyl acrylate: Role of a bifunctional La(O- i Pr)<inf>3</inf>/linked-BINOL complex 査読有り 国際誌

    Yukawa T., Seelig B., Xu Y., Morimoto H., Matsunaga S., Berkessel A., Shibasaki M.

    Journal of the American Chemical Society   132 ( 34 )   11988 - 11992   2010年09月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    The catalytic asymmetric aza-Morita-Baylis-Hillman reaction using unactivated methyl acrylate is described. A simple Lewis acidic metal catalyst, such as La(OTf)3, was not suitable for the reaction, but rare earth metal alkoxide/linked-BINOL complexes possessing bifunctional Lewis acid and Brønsted base properties efficiently promoted the reaction in combination with an achiral nucleophilic organocatalyst. The combined use of a La(O-iPr)3/(S,S)-TMS-linked-BINOL complex with a catalytic amount of DABCO promoted the aza-Morita-Baylis-Hillman reaction of a broad range of N-diphenylphosphinoyl imines. Products from aryl, heteroaryl, and alkenyl imines were obtained in 67-99% yield and 81-95% ee. It is noteworthy that isomerizable alkyl imines could be employed as well, giving products in 78-89% yield and 94-98% ee. Initial rate kinetic studies as well as kinetic isotope effect experiments using α-deuterio-methyl acrylate support the importance of both the nucleophilicity of La-enolate and the Brønsted basicity of a La-catalyst for promoting the reaction. © 2010 American Chemical Society.

    DOI: 10.1021/ja103294a

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  • Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of α-isothiocyanato esters with ketones 査読有り 国際誌

    Yoshino T., Morimoto H., Lu G., Matsunaga S., Shibasaki M.

    Journal of the American Chemical Society   131 ( 47 )   17082 - 17083   2009年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    (Chemical Equation Presented) Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of α-substituted α-isothiocyanato esters with unactivated simple ketones is described. A Bu2Mg/Schiff base catalyst promoted the aldol addition/cyclization sequence at room temperature, giving protected α-amino-β-hydroxy esters with contiguous tetrasubstituted chiral carbon stereocenters in 99 to 68% yield, 98:2 to 74:26 dr, and 98 to 82% ee. © 2009 American Chemical Society.

    DOI: 10.1021/ja908571w

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  • Mixed La-Li heterobimetallic complexes for tertiary nitroaldol resolution 査読有り 国際誌

    Hara K., Tosaki S., Gnanadesikan V., Morimoto H., Harada S., Sugita M., Yamagiwa N., Matsunaga S., Shibasaki M.

    Tetrahedron   65 ( 26 )   5030 - 5036   2009年06月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Full details of the kinetic resolution of tertiary nitroaldols derived from simple ketones are described. Mixed BINOL/biphenol La-Li heterobimetallic complexes gave the best selectivity in retro-nitroaldol reactions of racemic tertiary nitroaldols. Using a 2:1 mixture of La-Li3-(binaphthoxide 1a)3 complex (LLB) and La-Li3-(biphenoxide 1e)3 complex, chiral tertiary nitroaldols were obtained in 80-97% ee and 30-47% recovery yield. Transformations of products were also investigated. © 2009 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.tet.2009.02.031

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  • Lewis base assisted Brønsted base catalysis: Bidentate phosphine oxides as activators and modulators of brønsted basic lanthanum-aryloxides 査読有り 国際誌

    Morimoto H., Yoshino T., Yukawa T., Lu G., Matsunaga S., Shibasaki M.

    Angewandte Chemie - International Edition   47 ( 47 )   9125 - 9129   2008年11月

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    担当区分:筆頭著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    (Chemical Equation Presented) Dynamic Duo: A Lewis basic bidentate phosphine oxide was effective for activating and modulating the properties of Brønsted basic lanthanum aryl oxides. The Lewis base 1/lanthanum aryl oxide system was suitable for anti-selective Mannich-type reactions of trichloromethyl ketones (see scheme), affording unique building blocks for azetidine-2-carboxylic acids as well as β-amino acids. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.200803682

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  • Chiral γ-amino amide synthesis by heterobimetallic lanthanum/lithium/pybox-catalyzed direct asymmetric Mannich-type reactions of α-keto anilides 査読有り 国際誌

    Lu G., Morimoto H., Matsunaga S., Shibasaki M.

    Angewandte Chemie - International Edition   47 ( 36 )   6847 - 6850   2008年08月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    (Chemical Equation Presented) Not so Mannich now: A heterobimetallic La/Li/pybox complex was key in direct catalytic asymmetric Mannich-type reactions, using α-keto anilides as synthetic homoenolate equivalents to afford γ-amino amide products in up to > 99% yield, 95% ee, and >97:3 syn-selectivity. Stereoselective reduction of the α-keto moiety afforded the β-alkyl-γ-amino-α-hydroxy amide with three contiguous stereocenters (PG=protecting group). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.200801564

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  • A bench-stable homodinuclear Ni<inf>2</inf>-Schiff base complex for catalytic asymmetric synthesis of α-tetrasubstituted anti-α,β- diamino acid surrogates 査読有り 国際誌

    Chen Z., Morimoto H., Matsunaga S., Shibasaki M.

    Journal of the American Chemical Society   130 ( 7 )   2170 - 2171   2008年02月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Catalytic asymmetric direct Mannich-type reactions of α-substituted nitroacetates using a new bench-stable homodinuclear Ni2-Schiff base 1b complex are described. The Ni2-1b complex gave Mannich products, precursors for anti-α,β-diamino acids with an α-tetrasubstituted carbon stereocenter, in >99-91% ee. The Ni2-1b complex was also applicable to direct Mannich-type reactions of malonates and β-keto ester, giving products in high stereoselectivity (up to 99% ee, dr >97:3). Preliminary mechanistic studies suggested that the dinuclear Ni metal centers had key roles to achieve good reactivity and high stereoselectivity. Copyright © 2008 American Chemical Society.

    DOI: 10.1021/ja710398q

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  • Organolithiums and lithium 2,2,6,6-tetramethylpiperidide in reductive alkylation of epoxides: Synthesis of (E)-alkenes [(E)-2-methyltetradeca-1,3-diene] 国際誌

    Hodgson D.M., Humphreys P.G., Fleming M.J., Morimoto H., Mihara H., Shibasaki M.

    Organic Syntheses   85   1 - 9   2008年01月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    DOI: 10.15227/orgsyn.085.0001

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  • Lanthanum aryloxide/pybox-catalyzed direct asymmetric mannich-type reactions using a trichloromethyl ketone as a propionate equivalent donor 査読有り 国際誌

    Morimoto H., Lu G., Aoyama N., Matsunaga S., Shibasaki M.

    Journal of the American Chemical Society   129 ( 31 )   9588 - 9589   2007年08月

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    担当区分:筆頭著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Direct catalytic asymmetric Mannich-type reaction of a trichloromethyl ketone as a propionate equivalent donor is described. A new lanthanum aryloxide-iPr-pybox + lithium aryloxide combined catalyst was the most effective, promoting the reaction of N-2-thiophenesulfonyl imines with the trichloromethyl ketone. syn-Mannich adducts were obtained from various aryl, heteroaryl, alkenyl, and alkyl imines in > 99-72% yield, syn/anti of > 30:1-8:1, and 98-92% ee (from a propionate equivalent donor) using 2.5-10 mol % catalyst. The Mannich adduct was converted not only into ester but also into useful building blocks. Copyright © 2007 American Chemical Society.

    DOI: 10.1021/ja073285p

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  • Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes 査読有り 国際誌

    Kakei H., Tsuji R., Ohshima T., Morimoto H., Matsunaga S., Shibasaki M.

    Chemistry - An Asian Journal   2 ( 2 )   257 - 264   2007年07月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    The full details of the asymmetric epoxidation of α,β- unsaturated esters catalyzed by yttrium complexes with biaryldiol ligands are described. An yttrium-biphenyldiol catalyst, generated from Y(OiPr) 3-biphenyldiol ligand-triphenylarsine oxide (1:1:1), is suitable for the epoxidation of various α,β-unsaturated esters. With this catalyst, β-aryl α,β-unsaturated esters gave high enantioselectivities and good yields (≤99% ee). The reactivity of this catalyst is good, and the catalyst loading could be decreased to as little as 0.5-2 mol % (the turnover number was up to 116), while high enantiomeric excesses were maintained. For β-alkyl α,β-unsaturated esters, an yttrium-binol catalyst, generated from Y-(OiPr)3-binol ligand-triphenylphosphine oxide (1:1:2), gave the best enantioselectivities (≤97% ee). The utility of the epoxidation reaction was demonstrated in an efficient synthesis of (-)-ragaglitazar, a potential antidiabetes agent. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/asia.200600309

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  • Catalytic asymmetric Michael reactions of dibenzyl malonate to α,β-unsaturated N-acylpyrroles using a La(O-iPr)<inf>3</inf>/Ph-linked-BINOL complex 査読有り 国際誌

    Park S.Y., Morimoto H., Matsunaga S., Shibasaki M.

    Tetrahedron Letters   48 ( 16 )   2815 - 2818   2007年04月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Catalytic asymmetric Michael reactions of a malonate to acyclic α,β-unsaturated N-acylpyrroles as ester equivalent acceptors are described. A La(O-iPr)3/(S,S)-linked-BINOL complex, which is suitable for Michael addition to cyclic enones, is not suitable for acyclic α,β-unsaturated N-acylpyrroles. A new (S,S)-Ph-linked-BINOL chiral ligand was developed to improve enantioselectivity, and a La(O-iPr)3/(S,S)-Ph-linked-BINOL complex with the addition of HFIP afforded Michael adducts in good yield and enantioselectivity (up to 96% ee). © 2007 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.tetlet.2007.02.112

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  • Catalytic asymmetric epoxidation of α-methyl α,β- unsaturated anilides as ester surrogates 査読有り 国際誌

    Chen Z., Morimoto H., Matsunaga S., Shibasaki M.

    Synlett   ( 20 )   3529 - 3532   2006年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Catalytic asymmetric epoxidation of α-methyl α,β- unsaturated carboxylic acid derivatives was achieved using anilide as a template. The Pr(Oi-Pr)3-6,6́-Ph-BINOL complex (10 mol%) with a Ph3P(O) (30 mol%) additive promoted the epoxidation of anilides in up to 99% yield and 88% ee. For α-methyl-β-Ph α,β- unsaturated anilide, the Gd(Oi-Pr)3-6,6′-I-BINOL complex (10 mol%) with Ar3P(O) (30 mol%, Ar = 4-methoxyphenyl) was suitable, giving epoxide in 87% yield and 78% ee. © Georg Thieme Verlag Stuttgart.

    DOI: 10.1055/s-2006-956491

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  • Mixed La-Li heterobimetallic complexes for tertiary nitroaldol resolution 査読有り 国際誌

    Tosaki S., Hara K., Gnanadesikan V., Morimoto H., Harada S., Sugita M., Yamagiwa N., Matsunaga S., Shibasaki M.

    Journal of the American Chemical Society   128 ( 36 )   11776 - 11777   2006年09月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    A kinetic resolution of tertiary nitroaldols derived from simple ketones is described. Mixed BINOL/biphenol La-Li heterobimetallic complexes gave the best selectivity in retro-nitroaldol reactions of racemic tertiary nitroaldols. By using a mixture of La-Li3-(1a)3 complex (LLB 2a) and La-Li3-(1b)3 (LLB* 2b) complex in a ratio of 2/1, chiral tertiary nitroaldols were obtained in 80-97% ee and 30-47% recovery yield. Copyright © 2006 American Chemical Society.

    DOI: 10.1021/ja064858l

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  • Trichloromethyl ketones as synthetically versatile donors: Application in direct catalytic mannich-type reactions and the stereoselective synthesis of azetidines 査読有り 国際誌

    Morimoto H., Wiedemann S., Yamaguchi A., Harada S., Chen Z., Matsunaga S., Shibasaki M.

    Angewandte Chemie - International Edition   45 ( 19 )   3146 - 3150   2006年05月

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    担当区分:筆頭著者   記述言語:英語   掲載種別:研究論文(学術雑誌)

    Chemical transformers! Catalytic nucleophilic activation of trichloromethyl ketones allows applications in intermolecular carbon-carbon bond-forming reactions. Mannich adducts such as azetidines can be obtained from the primary products in high yield and syn selectivity. PG = protecting group. (Chemical Equation Presented) © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.200600227

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  • Non-C<inf>2</inf>-symmetric, chirally economical, and readily tunable linked-binols: Design and application in a direct catalytic asymmetric mannich-type reaction 査読有り 国際誌

    Yoshida T., Morimoto H., Kumagai N., Matsunaga S., Shibasaki M.

    Angewandte Chemie - International Edition   44 ( 22 )   3470 - 3474   2005年05月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    (Chemical Equation Presented) An achiral unit is shown to be better than a chiral unit in promoting an asymmetric reaction. Non-C2-symmetric linked-binols 1 with one chiral 1,1′-bi-2-naphthol unit and one flexible achiral unit are employed as ligands in direct catalytic asymmetric Mannich-type reactions (see scheme; TON = turnover number). With as little as 0.01 mol% of ligand 1 a and 0.04 mol% of Et2Zn, the reaction proceeded smoothly to give the product in 98% ee. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.200500425

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  • Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et<inf>2</inf>Zn/linked-BINOL complex: Synthesis of either anti- or syn-β-amino alcohols 査読有り 国際誌

    Matsunaga S., Yoshida T., Morimoto H., Kumagai N., Shibasaki M.

    Journal of the American Chemical Society   126 ( 28 )   8777 - 8785   2004年07月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)

    Full details of a direct catalytic asymmetric Mannich-type reaction of a hydroxyketone using a Et2Zn/(S,S)-linked-BINOL complex are described. By choosing the proper protective groups on imine nitrogen, either anti- or syn-β-amino alcohol was obtained in good diastereomeric ratio, yield, and excellent enantiomeric excess using the same zinc catalysis. N-Diphenylphosphinoyl (Dpp) imine 3 gave anti-β-amino alcohols in anti/syn = up to >98/2, up to >99% yield, and up to >99.5% ee, while Boc-imine 4 gave syn-β-amino alcohols in anti/syn = up to 5/95, up to >99% yield, and up to >99.5% ee. The high catalyst turnover number (TON) is also noteworthy. Catalyst loading was successfully reduced to 0.02 mol % (TON = up to 4920) for the anti-selective reaction and 0.05 mol % (TON = up to 1760) for the syn-selective reaction. The Et2Zn/(S,S)-linked-BINOL complex exhibited far better TON than in previous reports of catalytic asymmetric Mannich-type reactions. Mechanistic studies to clarify the reason for the high catalyst efficiency as well as transformations of Mannich adducts are also described.

    DOI: 10.1021/ja0482435

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▼全件表示

著書

  • Development and Integration of New Green Reactions 査読有り

    Ohshima T., Morimoto H., Kadota T.(共著)

    Middle Molecular Strategy: Flow Synthesis to Functional Molecules  2021年01月  ( ISBN:9789811624575

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    記述言語:英語

    Over the last few decades, the quest for environmentally benign chemical transformations has become an important topic in both industrial and academic research. An integrated synthesis that combines multiple reactions in a single operation in a one-pot or a flow system without isolating intermediates has recently drawn much attention as a replacement for conventional step-by-step synthesis. Because in the reaction integration process the reaction mixtures are directly used to the next reaction without purification and the generated co- and by-products may have negative effects on the next reaction, integrating highly atom-economical reactions is quite important. To this end, we developed several highly atom-economical direct catalytic reactions. In this review, we focused on the developments of synthesis and reactions of N-unprotected ketimines and their applications for time integration (one-pot sequential process through N-unprotected ketimine synthesis).

    DOI: 10.1007/978-981-16-2458-2_15

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