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

DOI： 10.1002/ejoc.202301130

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担当区分：最終著者,　責任著者   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/chemistry5040177

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

In this work, a straightforward synthesis of C3-N1' bisindolines is achieved by a formal umpolung strategy. The protocols were tolerant of a wide variety of substituents on the indole and indoline ring. In addition, the C3-N1' bisindolines could be converted to C3-N1' indole-indolines and C3-N1'-bisindoles. Also, we have successfully synthesized (±)-rivularin A through a biomimetic late-stage tribromination as a key step.

DOI： 10.1002/chem.202302963

PubMed

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

DOI： 10.1021/acs.joc.3c00691

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.joc.3c00013

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：MDPI AG  

C3–N1′ bond formation of bisindoles has been a great challenge due to the intrinsic reactivity of indoles as both C3 and N1-nucleophilic character. Herein, we demonstrate an C3–N1′ cross-coupling reaction of indoles using N-methoxyindoles as N-electrophilic indole reagents in the presence of Lewis acid. The bisindoles generated in this transformation are latent C3-nucleophile, allowing them to be used as strategic intermediates in sequential C3–N1′–C3′–N1″ triindole formations. The potential synthetic usefulness of this sequential transformation was highlighted upon application to the construction of C3–N1 looped polyindoles.

DOI： 10.3390/chemistry5010033

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

DOI： 10.3390/IJMS24054411

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.joc.2c02561

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D3RA90053C

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：MDPI AG  

(1) Background: Japanese Kampo medicine has its origin in ancient Chinese medicine. In 742, a Tang Dynasty monk named Jianzhen (Ganjin) was invited by Japanese clerics to visit Japan and teach commandments in Buddhism. Because of the dangers of the voyage and also other obstacles, he took 11 years to reach Japan on the sixth voyage and he was blind when he arrived in Japan. He was the first person in China to go to Japan to establish the Buddhism commandments, and he was also the first person in Japan to directly teach traditional Chinese medicine. Until now, there have been few reports in English about the details of the Chinese herbal medicines he brought to Japan, including the types of herbal medicines, pharmacological activities, and formulations. In the review, we systematically and comprehensively summarized Jianzhen’s life from the standpoint of his medical and pharmaceutical knowledge and the types and pharmacological activities of Chinese herbal medicines and prescriptions that were brought to Japan by Jianzhen; (2) Methods: A review was made on the relevant literature written by Chinese, Japanese, and English languages regarding the medical and pharmacological knowledge of Jianzhen, the 36 Chinese herbal medicines brought to Japan by Jianzhen, and the pharmacological and therapeutic effects of these 36 herbal medicines, as well as their formulations; (3) Results: The review of the literature proved that Jianzhen’s prescriptions served as a basis for current herbal medicines (Kampo) in Japan. In the process of the literature search, we found a book entitled Jianshangren (Holy Priest Jianzhen)’s Secret Prescription, which recorded the complete prescription of the 36 traditional Chinese medicines Jianzhen brought to Japan; (4) Conclusions: Jianzhen is one of the ancestors of traditional Chinese medicine/Kampo medicine, and he brought traditional Chinese medicine and medical books to Japan for patients. He made important contributions to the development of traditional Chinese medicine in Japan.

DOI： 10.3390/compounds2040022

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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）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.jnatprod.2c00559

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Organic & Biomolecular Chemistry  

<jats:p>We would like to take this opportunity to highlight the Outstanding Reviewers for <jats:italic>Organic &amp; Biomolecular Chemistry</jats:italic> in 2021, as selected by the editorial team for their significant contribution to the journal.</jats:p>

DOI： 10.1039/D2OB90069F

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担当区分：筆頭著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.202201113

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記述言語：英語  

DOI： 10.1021/acs.orglett.2c00370

J-GLOBAL

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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）   出版者・発行元：Royal Society of Chemistry ({RSC})  

We have developed an efficient reaction of 3-azido-2-methoxyindolines with <italic>O</italic>-nucleophiles in the presence of a Lewis acid, affording 2-monoacyloxy or alkoxy indolin-3-ones.

DOI： 10.1039/D2QO00048B

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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）  

DOI： 10.1039/d1cc06033c

PubMed

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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）  

We introduce readily available ammonium hemiaminals as O-transfer reagents and commercially available acetonitriles as a primary amide enolate precursor. The combination serves as an amide enolate equivalent, thereby providing one-pot access to α-substituted indolylacetamides. A broad substrate scope and good functional group tolerance as well as gram-scale synthesis make this protocol highly attractive. Mechanistic experiments suggest that the cyano group is trapped by a hydroxy group of hemiaminals en route to the desired primary amides under metal-free conditions.

DOI： 10.1039/d1cc02821a

PubMed

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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）   出版者・発行元：ROYAL SOC CHEMISTRY  

Enamines undergo alpha-indolization with ammonium salts in the presence of Et3N to form alpha-indolylketones. This is the first example of transition metal-, oxidant-, and fluorous solvent-free alpha-indolization of ketones. Key to the success of this convenient protocol was the use ofin situgenerated electrophilic indole species, as well as the use of enamines as a ketone enolate equivalent.

DOI： 10.1039/d0cc04795c

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担当区分：最終著者,　責任著者   記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.14894/faruawpsj.56.8_757

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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）  

<p>One-pot synthesis of indole-fused bicyclo[2.2.2]octanones from DiMeOIN and 2-cyclohexen-1-one are accomplished under iodine catalyst. This simple and metal-free conditions provides a practical tool to construct Csp3-rich complex molecules via oxidative...</p>

DOI： 10.1039/d0ob01038c

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担当区分：最終著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/D0CC01210F

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

DOI： 10.3987/com-19-s(f)19

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担当区分：筆頭著者,　責任著者   記述言語：日本語   出版者・発行元：公益社団法人 有機合成化学協会  

<p>C3-Nucleophilic substitution of indoles has been limited because the transformation requires an umpolung of the C3 position of indoles. Among the indole derivatives, indole-2,3-epoxides could be potentially be used as C3-electrophilic reagents due to the electrophilic nature of the C2 and C3 positions. However, their use as C3 electrophilic reagents has not been possible so far due to their instability.</p><p>We describe a novel and bench stable surrogate of indole-2,3-epoxide, 2-hydroxyindoline-3-triethylammonium bromide (HITAB), which was found to be a convenient reagent for formal C3-electrophilic reactions of indoles with nucleophiles. By taking advantage of the nucleophilic character of the oxygen of the 2-hydroxyindoline, interrupted retro-Claisen and interrupted Feist-Bénary reactions with 1,3-dicarbonyl compounds, one-pot formation of furodiindolines from 3-substituted indoles were achieved. Furthermore, we developed a novel cascade reaction of the indole-2,3-epoxide surrogate with γ-carbolines to access multiheterocyclic compounds containing both isotryptamines and pyrimido［1,6-<i>a</i>］indoles. This reaction utilizes the <i>in situ</i> formation of a bulky quaternary ammonium salt via ammonium exchange, which undergoes Hofmann elimination/vinylogous Mannich/retro-Mannich/cyclization cascade sequences. The synthetic potential of the ammonium salts was demonstrated by the short synthesis of cryptolepine, iheyamine A, racemocine B derivative, and neocryptolepine derivative.</p>

DOI： 10.5059/yukigoseikyokaishi.78.597

CiNii Article

CiNii Books

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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）  

The regioselective synthesis of both 2- and 3-alkoxyindoles from a common intermediate, 2-alkoxy-3-bromoindolines (ROBIN), is described. The 2-alkoxyindoles are obtained by a base-promoted regioselective elimination of HBr from ROBIN, whereas the synthesis of 3-alkoxyindoles is achieved by a silver-mediated alkoxylation followed by an acid-promoted elimination of alkoxide. This key elimination features the complete regioselectivity and no need for catalysts, that makes it have potential synthetic applications. Furthermore, this protocol is user friendly because ROBIN is able to be prepared from commercially available indoles and is a bench-stable easy-to-handle crystalline substrate, thus allowing the concise synthesis of a variety of both 2- and 3-alkoxyindoles.

DOI： 10.1248/cpb.c20-00135

PubMed

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0ob01038c

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/D0OB01038C

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担当区分：最終著者,　責任著者   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0039-1690734

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

DOI： 10.1002/hlca.201900116

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

DOI： 10.3987/com-19-14077

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担当区分：筆頭著者,　責任著者   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.orglett.9b01108

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担当区分：筆頭著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.orglett.8b04120

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担当区分：筆頭著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：Japan Institute of Heterocyclic Chemistry  

DOI： 10.3987/com-18-s(f)30

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担当区分：最終著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/C9RA02321F

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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）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.orglett.8b00332

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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）   出版者・発行元：American Chemical Society  

A concise synthesis of the azepinobisindole alkaloid iheyamine A from an indole-2,3-epoxide equivalent has been achieved. This method features a formal C3 electrophilic reaction of an indole-2,3-epoxide equivalent with tryptamine to form a 3-aminoindoline and a novel In-catalyzed dehydrative Mannich-type reaction of the hemiaminal to give the azepinobisindole core.

DOI： 10.1021/acs.orglett.8b00330

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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）   出版者・発行元：Wiley Blackwell  

Phaitanthrin E was biomimetically synthesized from methyl indole-3-carboxylate and methyl anthranilate or anthranilic acid using the ester group as an activating group. The reaction proceeds through NCS-mediated dearomatization/TFA-catalyzed protonation of indolenine/C(2) amination/Et3N-promoted aromatization and cyclization in one-pot procedure. This method is capable of converting simple biomass materials to phaitanthrin E. The synthesis not only allows assessment of antiproliferative activity, but also affords experimental support for the hypothetical biosynthetic pathway of phaitanthrin E. The resulting phaitanthrin E derivatives were evaluated for in vitro antiproliferative activity against human colorectal cancer cells (DLD-1). The biogenetic intermediate of phaitanthrin E showed higher antiproliferative activity than the natural product, phaitanthrin E. Furthermore, a concise synthesis of tryptanthrin is also accomplished from indole-3-carbaldehyde and methyl anthranilate using the aldehyde group as an activating group.

DOI： 10.1002/hlca.201700284

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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：研究論文（学術雑誌）   出版者・発行元：Japan Institute of Heterocyclic Chemistry  

An acetyl chloride/NaI-mediated Nazarov-type cyclization of an indolyl vinyl ketone was developed to give a cyclopenta[b]indole in high yield. An acyl Finkelstein reaction is a key feature for this unprecedented Nazarov-type cyclization.

DOI： 10.3987/COM-18-13866

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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   出版者・発行元：公益社団法人 有機合成化学協会  

<p>We describe the total synthesis of indolo[2,1-b]quinazoline alkaloids tryptanthrin (1a), candidine (2), phaitanthrins A (3), B (4), C (5), cruciferane (8), and cephalanthrin A (9) using oxidative cascade sequences as the key step. Phaitanthrin E (7a) was synthesized by a novel methodology that features a concise approach involving the intermolecular condensation and intramolecular aryl C-H amination mediated by Cu-complexes to construct the indolo[2,1-b]quinazoline core. Moreover, an acid catalyzed one-pot synthesis of phaitanthrin E (7a) via intermolecular amination/intramolecular cyclization cascade using NCS was also developed.</p>

DOI： 10.5059/yukigoseikyokaishi.76.802

CiNii Article

CiNii Books

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担当区分：筆頭著者,　責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：Japan Institute of Heterocyclic Chemistry  

DOI： 10.3987/com-17-s(t)15

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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）   出版者・発行元：ROYAL SOC CHEMISTRY  

We have developed a self-relay copper(I)-catalyzed Ullmann N-arylation/2-amidation cascade to form functionalized indolo[1,2-a]quinazolinones in one-pot from easily available indoles with 2-bromobenzamides. This novel transformation features a tandem process of Ullmann-type coupling, activation of indolenine, and 2-amidation in the presence of a single copper catalyst. In addition, among the substituents of indoles at the C3 position, methyl carboxylate could act as an activating group in this Ullmann N-arylation/2-amidation cascade.

DOI： 10.1039/c7qo00549k

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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）   出版者・発行元：Thieme Publishing Group  

DOI： 10.1055/s-0036-1588438

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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）   出版者・発行元：AMER CHEMICAL SOC  

A novel indole-2,3-epoxide equivalent, 2-hydroxyindbline-3-triethylammonium bromide, was found, to be a convenient reagent for formal C3-electrophilic reactions of indoles with various nudeophiles. By taking advantage of the nudeophilie character of the oxygen of the 2-hydroxyindo-line the interrupted retro-Claisen interrupted Feist - Benary reactions, with 1,3-dicarbonyl compounds Were efficiently achieved.

DOI： 10.1021/acs.orglett.7b01940

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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）   出版者・発行元：ROYAL SOC CHEMISTRY  

We have developed a copper-catalyzed Ritter-type reaction/cyclization cascade of anthranilic acids and nitriles, affording the quinazolin-4(3H)-ones. The cascade proceeds through a Ritter-type reaction capturing the iminoketene intermediates by nitriles. Furthermore, we found a novel Ritter-type reaction/condensation/intramolecular anti-Markovnikov hydroamination cascade, providing access to functionalized diazocines in one-pot.

DOI： 10.1039/c7cc01406f

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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）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.jnatprod.7b00008

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掲載種別：研究論文（学術雑誌）  

©2017 The Japan Institute of Heterocyclic Chemistry. We investigated the one-pot synthesis of several fused 2-pyridone ring systems based on a Curtius rearrangement, followed by a microwave-assisted thermal electrocyclization of a 2-aza-6?-electron system including isocyanate. We synthesized seven heterocyclic compounds containing a fused 2-pyridone ring. In these results, the one-pot synthesis of fused 2-pyridone ring system 5 from (E)-acrylic acids 1 under microwave irradiation conditions was more effective than the conventional reaction conditions in terms of the yield and the reaction time.

DOI： 10.3987/COM-16-S(S)13

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掲載種別：研究論文（学術雑誌）  

DOI： 10.3987/COM-16-S(S)5

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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）   出版者・発行元：AMER CHEMICAL SOC  

We have developed a concise one-pot synthesis of phaitanthrin E derivatives, where simple starting materials undergo an acid-catalyzed intermolecular amination/intramolecular cyclization cascade.

DOI： 10.1021/acs.orglett.6b03466

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER FRANCE-EDITIONS SCIENTIFIQUES MEDICALES ELSEVIER  

We report a convenient synthesis of carbazole-1,4-quinone alkaloid koeniginequinones A and B using a tandem ring-closing metathesis with the dehydrogenation reaction sequence under an O-2 atmosphere as an important step. Using this method, carbazole-1,4-quinones substituted at the 5-, 6-, 7-, and/or 8-positions have been synthesized. Moreover, 24 compounds, including koeniginequinones A and B, have been evaluated for their antiproliferative activity against HCT-116 and HL-60 cells, and the 6-nitro analog exhibited the most potent activity against both tumor cell types. (C) 2016 Elsevier Masson SAS. All rights reserved.

DOI： 10.1016/j.ejmech.2016.05.065

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掲載種別：研究論文（学術雑誌）  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A one-pot synthesis of phaitanthrin E starting from methyl indole-3-carboxylate and isatoic anhydride through intermolecular condensation/intramolecular aryl C-H amination cascade was developed.

DOI： 10.3987/COM-16-13465

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Copyright © 2016 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim. Concise syntheses of 9-methoxyellipticine, 3,4-dihydroellipticine (μ-alkaloid D), 1,2,3,4-tetrahydroellipticine, 2-methyl-1,2,3,4-tetrahydroellipticine, olivacine, 3,4-dihydroolivacine, (±)-guatambuine, and (±)-janetine were developed starting from hexatriene intermediates readily obtained by Pd-catalyzed tandem cyclization/cross-coupling reaction of indolylborates. The route enables the facile construction of pyrido[4,3-b]carbazoles by Cu-catalyzed 6π-electrocyclization and subsequent transformation of the pyridocarbazole intermediates into pyrido[4,3-b]carbazole alkaloids. Concise total syntheses of pyrido[4,3-b]carbazole alkaloids were accomplished using Cu-catalyzed 6π-electrocyclization of hexatriene as a key step.

DOI： 10.1002/ejoc.201600246

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Total syntheses of koeniginequinones A and B, isolated from Murraya koenigii, were newly achieved by constructing of carbazole-1,4-quinone using a one-pot Pd-catalyzed cyclocarbonylation method with 2-(but-2-en-l-y1)-3-iodoindoles derived from known methyl 6-methoxyindole-2-carboxylate and methyl 5,6-dimethoxyindole-2-carboxylate, followed by desilylation, and an oxidation sequence.

DOI： 10.3987/COM-15-S(T)5

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担当区分：筆頭著者   記述言語：日本語   出版者・発行元：社団法人 有機合成化学協会  

In our continuing study of the reactivity and synthetic application of indolylborate as a versatile synthetic intermediate, we found that the use of indolylborate in palladium-catalyzed cross-coupling reaction is highly effective for the synthesis of indole derivatives. The present account deals with the results concerning a novel approach to indole alkaloids based on the use of the palladium-catalyzed cross-coupling. Dimeric indole alkaloid, yuechuke, was synthesized through the palladium-catalyzed carbonylative cross-coupling reaction. Pyridocarbazole alkaloids (ellipticine, olivacine, and their related alkaloids), and indolophenanthridine alkaloid (calothrixins A and B) were obtained by the use of cyclization/cross-coupling domino reaction. In addition, (CuOTf)2·toluene complex was demonstrated to catalyze 6π-electrocyclization of hexatrienes, leading to pyrido [4,3-b] carbazoles.

DOI： 10.5059/yukigoseikyokaishi.74.117

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A one-pot conversion of skatole to tryptanthrin, an indolo[2,1-b]quinazoline alkaloid, was achieved by Cu-mediated oxidation.

DOI： 10.3987/COM-15-13228

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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）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The palladium-catalyzed intramolecular oxidative coupling reaction of 1,1'-carbonyldiindoles was achieved by using Pd(OAc)(2) and Cu(OAc)(2), producing 1,1'-carbonyl-2,2'-biindolyls, which were then converted to tjipanazoles D and I

DOI： 10.3987/COM-14-S(K)28

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記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

This review covers the literature on simple indole alkaloids and those with a nonrearranged monoterpenoid unit from the beginning of 2012 up to the end of 2013, which includes newly isolated alkaloids, structure determinations, total syntheses and biological activities.

DOI： 10.1039/c5np00032g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SPRINGER BIRKHAUSER  

Calothrixin B, whose structure consists of a pentacyclic indolo[3,2-j] phenanthridine framework, was originally isolated as a secondary metabolite from Calothrix cyanobacteria and was found to exhibit potent antiproliferative activity. In this study, treatment with 100 mu M of calothrixin B did not inhibit the proliferation of HL-60 promyelocytic leukemia cells, the result indicated that calothrixin B could possess weaker activity against leukemia cells. In a previous study of the structure-antiproliferative activity relationships of calothrixin B analogs, the tetracyclic 5H-pyrido[4,3-b] carbazole-4,11(6H)-dione structure, which does not include the benzene ring found in calothrixin B, was reported to be necessary for antiproliferative activity; however, the induction of substituents on the indole nitrogen atom of calothrixin B decreased the antiproliferative activity of the compound. To develop calothrixin B analogs with good antiproliferative activity against both HL-60 and HCT-116 cells, we synthesized various N-substituted calothrixin B analogs and assessed their activity. Compared with calothrixin B, N-OMe calothrixin B displayed almost the same or slightly stronger antiproliferative activity against HCT-116 cells, whereas the N-MOM analog demonstrated slightly weaker activity against these cells. These two analogs also inhibited proliferation of HL-60 cells, whereas calothrixin B did not exhibit antiproliferative activity toward these cells. Among calothrixin B analogs, N-OMe and N-MOM calothrixins B are cytotoxic against HCT-116 cells and not the lack of the effect on HL-60 cells.

DOI： 10.1007/s00044-014-1061-6

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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）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A one-pot approach to indolo[2,1-b]quinazolines from indole-3-carbaldehydes through the Dakin oxidation was developed. It was shown that the reaction proceeded through the condensation of indole-3-carbaldehydes with isatoic anhydrides, derived in situ from indole-3-carbaldehydes by the Dakin oxidation, and further oxidation/cyclization steps. (C) 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2014.07.113

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

novel one-pot synthesis of carbazole-1,4-quinone by consecutive Pd-catalyzed cyclocarbonylation, desilylation, and oxidation reactions is described. We propose a possible mechanism of the cyclocarbonylation reaction between 3-iodo-2-propenylindole and CO (1 atm) in the presence of a tributyl(vinyl)tin and Pd-catalyst and the resulting acylpalladium species was directly coupled with a terminal alkene to produce the carbazole-1,4-quinone. To our knowledge, this is the first example of this type of reaction. A new formal total synthesis of a carbazole-1,4-quinone alkaloid, murrayaquinone A was established using this reaction. (C) 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2014.01.015

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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）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A one-pot synthesis of 3,3'-bisindolylmethanes was developed through the intermolecular Pummerer reaction using indole as a nucleophile.

DOI： 10.3987/COM-13-S(S)31

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

9,10-Phenanthrenequinone (9,10-PQ) is one of the most abundant quinones among diesel exhaust particulates. Recent data have suggested that quinones induce apoptosis in immune, epithelial and tumor cells, leading to respirator illness; however, the mechanisms by which quinones induce apoptosis and the structure required for this remain unknown. We studied the antitumor activity of 9,10-PQ analogs against two human tumor cell lines, HCT-116 colon tumor cells and HL-60 promyelocytic leukemia cells. The loss of the cis-orthoquinone unit in 9,10-PQ abrogated its ability to induce apoptosis in the two tumor cell lines, and the LC50 values of these analogs were indicated over 10 mu M. An analog of 9,10-PQ in which the biaryl unit had been deleted displayed a reduced ability to induce tumor cell apoptosis, while the analogs 1,10-phenanthroline-5,6-dione (9) and pyrene-4,5-dione (10), which also had modified biaryl units, exhibited increased tumor cell apoptotic activity. The cis-orthoquinone unit in 9,10-PQ was identified as essential for its ability to induce apoptosis in tumor cells, and its biaryl unit is also considered to influence orthoquinone-mediated apoptotic activity. (C) 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmcl.2013.06.015

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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   出版者・発行元：The Society of Synthetic Organic Chemistry, Japan  

The development of biomimetic reactions is one of the major challenges for synthetic chemists, because mimicking these complicated reactions in the laboratory by simple catalytic systems is difficult to achieve in general. Vitamine B6-dependent aminotransferase-catalyzed transamination of α-keto acids from pyridoxamine is an important process to generate α-amino acids in nature. In this review, recent progresses on the biomimetic transamination of α-keto esters are described.

DOI： 10.5059/yukigoseikyokaishi.71.62

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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）  

A one-pot approach to 3,3′-bisindolylmethane derivatives from nitrobenzene derivatives through the Bartoli indole synthesis was developed, in which the acid used to quench the reaction markedly affected its outcome. Quenching the reaction with concd HCl produced 3,3′-bisindolylmethane in contrast to the formation of 7-substituted indole by quenching with NH 4Cl. © 2013 American Chemical Society.

DOI： 10.1021/ol401486s

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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   出版者・発行元：日本薬学会  

This review describes a synthesis of indole compounds using multifunctional synthons. The multifunctional synthons, trienes and gramines, were respectively synthesized using Pd-catalyzed tandem cyclization/cross-coupling reaction of indolylborate with vinyl bromide, and reaction of indolylcuprate with iminium chloride. As an application of the multifunctional synthons to the indole alkaloids synthesis, we accomplished the total synthesis of ellipticine, 9-methoxyellipticine, 9-hydroxyellipticine, tetrahydroellipticine, μ-alkaloid B, μ-alkaloid D, calothrixin A, calothrixin B, tubifoline, and yuehchukene. We have also developed 6π-electrocyclization of hexatrienes catalyzed by Cu(I) trifluoromethanesulfonate toluene complexe, which is unprecedented.

DOI： 10.1248/yakushi.12-00233

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記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

This review covers the literature on simple indole alkaloids and those with a non-rearranged monoterpenoid unit from the beginning of 2010 up to the end of 2011, which includes newly isolated alkaloids, structure determinations, total syntheses and biological activities.

DOI： 10.1039/c3np20118j

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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）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A short total synthesis of a bisindole alkaloid, yuechukene, was achieved through the dimerization of beta-dehydroprenylindole generated in situ from 1-(indol-3-yl)-3-methylbut-2-en-1-amine.

DOI： 10.3987/COM-12-S(N)49

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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）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The palladium-catalyzed tandem cyclization/cross-coupling reaction of triethyl(indol-2-yl)borate with vinyl bromide was successfully used in the concise total synthesis of the indolophenanthridine alkaloids, calothrixins A and B.

DOI： 10.1002/ejoc.201200657

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

We synthesized calothrixin B using our developed biomimetic method and derived N-alkyl-calothrixins A and B. The in vitro antimalarial activity of the calothrixin derivatives, including calothrixins A and B, against the Plasmodium falciparum FCR-3 strain was evaluated. All test compounds exhibited antimalarial activity over a concentration range of 6.4 x 10(-6)-1.2 x 10(-7) M. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmcl.2012.05.064

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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）   出版者・発行元：AMER CHEMICAL SOC  

The concise total synthesis of calothrixins A and B has been accomplished by utilizing the one-pot formation of hexatriene as a key intermediate via the palladium-catalyzed tandem cyclization/cross-coupling reaction of triethyl(indo1-2-yl)borate. In another key transformation, the indolo[3,2-j]phenanthridine core was prepared in high yield via Cu(I)-mediated 6 pi-electrocyclization.

DOI： 10.1021/ol201107a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A novel and simple protocol for the synthesis of 1-(2-aminoethyl)pyrano[3,2-e]indole derivatives has been developed using the Pictet-Spengler reaction of N-b-benzylserotonin with alpha,beta-unsaturated aldehydes in the presence of Et3N in 2-propanol or MeOH.

DOI： 10.3987/COM-11-12144

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Cu- and Rh-catalyzed coupling reactions of 2-azabicyclo[2.2.1]hept-5-en-3-ones (1) with arylboronic acids were successful carried out under microwave irradiation conditions and yielded N-aryl and C-aryl derivatives of 1, respectively.

DOI： 10.1002/ejoc.201000135

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

This review covers the literature on simple indole alkaloids and those with a nonrearranged monoterpenoid unit, and includes newly isolated alkaloids, structure determinations, total syntheses and biological activities.

DOI： 10.1039/c005345g

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

It was shown that dichloramine-T (1) reacted with cyclohexene in acetonitrile to give N&apos;-(2-chlorocyclohexyl) amidine 2a and N-(2-chlorocyclohexyl)acetamide (3) via the competitive addition of acetonitrile and N-chloro-N-tosylamino anion to cyclohexenechloronium ion. This reaction can be catalyzed by Cu(OAc)(2), primarily affording 2a. Furthermore, the resulting 2a can be cyclized to benzimidazol 14a in good yield by treating with KOH in dioxane.

DOI： 10.1002/hlca.200900214

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Quorum sensing (QS) systems have been discovered in a wide variety of bacteria, and mediate both intra- and interspecies communication. The AI-2-based QS system represents the most studied of these proposed interspecies systems and has been shown to regulate diverse functions such as bioluminescence, expression of virulence factors, and biofilm formation. As such, the development of modulatory compounds, both agonists and antagonists, is of great interest for the study of unknown AI-2-based QS systems and the potential treatment of bacterial infections. The fimbrolide class of natural products has exhibited excellent inhibitory activity against AI-2-based QS and as such may be considered the "gold standard" of AI-2 inhibitors. Thus, we sought to include a fimbrolide as a control compound for our recently developed alkyl-DPD panel of AI-2 modulators. Herein, we present a revised synthesis of a commonly studied fimbrolide as well as a direct comparison between the fimbrolide and alkyl-DPD analogues. We demonstrate that our alkyl-DPD analogues are more potent inhibitors of QS in both Vibrio harveyi and Salmonella typhimurium, the two organisms with defined AI-2 QS systems, and in doing so call into question the widely accepted use of fimbrolide-derived compounds as the "gold standard" of AI-2 inhibition.

DOI： 10.1021/ja9066783

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The reaction of Nβ-benzylserotonin with α,β-unsaturated and aryl aldehydes in the presence of a base produced 1H-azepino[5,4,3-cd]indoles. © 2009 The Japan Institute of Heterocyclic Chemistry All rights reserved.

DOI： 10.3987/COM-08-S(F)98

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その他リンク： http://orcid.org/0000-0003-1729-1097

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）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Rhodium-catalyzed arylation of 2-azabicyclo[2.2.1]hept-5-en-3-one was successfully performed by applying microwave irradiation.

DOI： 10.3987/COM-08-11483

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The palladium-catalyzed tandem cyclization-cross-coupling protocol using 1H-indol-2-yltrialkylborate (indolylborate) proved to be a versatile approach to the generation of 2-(4-piperidylmethyl)indole, which was successfully used for the preparation of (±)-tubifoline. © 2008 The Japan Institute of Heterocyclic Chemistry.

DOI： 10.3987/COM-07-11190

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その他リンク： http://orcid.org/0000-0003-1729-1097

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）  

Copper-catalyzed N-arylation reaction of 2-azabicyclo[2.2.1]hept-5-en-3-one (ABH) with arylboronic acids was successively performed in the presence of KOH and trimethylamine-N-oxide under microwave irradiation. © The Japan Institute of Heterocyclic Chemistry.

DOI： 10.3987/COM-07-S(N)6

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Palladium-catalyzed tandem cyclization - cross-coupling reaction of indolylborate 2 and vinyl bromide 5 was successfully applied in a short formal synthesis of olivacine. The reaction of 2 with 5 in the presence of Pd(OAc)(2) readily afforded three kinds of products, triene derivative 6 and vinylindole derivative 7, along with a small amount of the piperidine derivative 8 (Scheme 2). On the other hand, the reactions of 2 with bromide 10 or 15 were also examined (Schemes 4 and 5) and their outcome markedly depended oil the relative ease of ring closure as a function of ring size. Irradiation of 6 with a high-pressure pressure mercury lamp (-9; Scheme 2), followed by removal of the N-[(benzyloxy)carbonyl] group and subsequent oxidation afforded, after deprotection, pyridocarbazole 23, and the conversion of 23 to olivacine is known (Scheme 6).

DOI： 10.1002/hlca.200890195

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Catalytic asymmetric syntheses of (-)-centrolobine and (-)-de-O-methylcentrolobine have been achieved, incorporating a hetero-Diels-Alder (HDA) reaction between 4-aryl-2-silyloxy-1,3-butadienes and phenylpropargyl aldehyde derivatives as a key step. The HDA reaction using dirhodium(II) tetrakis[(R)-3-(benzene-fused-phthalimido)-2-piperidinonate], Rh-2(R-BPTPI)(4), as a chiral Lewis acid catalyst provides exclusively cis-2,6-disubstituted tetrahydropyran-4-ones in up to 93% ee. (C) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2007.09.003

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

[GRAPHICS]
Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh-2(S-FPTTL)(4), is an exceptionally efficient catalyst for enantioselective aminations of silyl enol ethers derived from acyclic ketones or a,beta-enones with [N-(2-nitrophenyisulfonyl)imino]phenyliodinane (NsN=IPh), providing N-(2-nitrophenyisulfonyl)-alpha-amino ketones in high yields and with enantioselectivities of up to 95% ee. The effectiveness of the present catalytic protocol has been demonstrated by an asymmetric formal synthesis of (-)-metazocine.

DOI： 10.1021/o1702019b

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その他リンク： http://orcid.org/0000-0003-1729-1097

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The enantioselective aziridination of alkenes with [N-(4-nitrophenylsulfonyl)imino]phenyliodinane catalyzed by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh-2(S-TCPTTL)(4), is described. While such enantioselectivities are highly dependent on the properties of the alkenes, 2,2-dimethylchromene was found to be a particularly suitable substrate which can be efficiently transformed into the aziridine product in 98% yield with 94% ee.

DOI： 10.3987/COM-07-S(K)63

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

The first successful example of the enantioselective intermolecular 1,3-dipolar cycloaddition of a chiral dirhodium(II) catalyst-associated carbonyl ylide with an aromatic aldehyde dipolarophile is described. The tandem carbonyl ylide formation/cycloaddition reactions of l-diazo-5-aryl-2,5-pentanediones with aromatic aldehydes using dirhodium(II) tetrakis[N-benzene-fused-phthaloyl- (S)-valinate] as a catalyst provide exclusively exo cycloadducts in up to 92% ee. © 2007 Wiley-VCH Verlag GmbH &amp; Co. KGaA,.

DOI： 10.1002/adsc.200600591

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Regioselectivity on the reaction of (1-methylindol-2-yl)cyanocuprate with N-(prop-2-en-1-ylidene)aminium chlorides was investigated.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PHARMACEUTICAL SOC JAPAN  

An efficient and reliable procedure for the preparation of dirhodium(II) tetrakis[N-phthaloyl-(S)-tert-leucinate], Rh-2(S-PTTL)(4), a universally effective catalyst for a range of enantioselective carbene transformations, is described. The N-phthaloylation of (S)-tert-leucine by the method of Bose with essentially no racemization is a key to this process.

DOI： 10.1248/cpb.53.1366

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記述言語：日本語   出版者・発行元：公益社団法人 有機合成化学協会  

DOI： 10.5059/yukigoseikyokaishi.78.637

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：日本語   出版者・発行元：公益社団法人 有機合成化学協会  

DOI： 10.5059/yukigoseikyokaishi.76.851

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記述言語：日本語   出版者・発行元：天然有機化合物討論会実行委員会  

【研究背景・目的】
アフリカ固有の灌木Cryptolepis sanguinolentaは、西アフリカ民族医学において、マラリア、細菌性呼吸器疾患、高血圧、下痢などの様々な病気の治療に使用されている重要な植物である。本植物の根の主成分であるcryptolepine (1) は、1931年に最初に単離されたインドロキノリンアルカロイドであり、その後、quindoline (2)、cryptolepinone (3)、11-isopropylcryptolepine (4)や、biscryptolepine (5)、cryptolepicarboline (6)、cryptoquindoline (7)、cryptospirolepine (8)といった二量体やスピロ体なども同植物から単離されている(Figure 1)。1,2) 特にcryptolepineへの関心は高く、本化合物をリードとする広範な研究により、抗マラリアをはじめ、抗腫瘍、抗炎症、降圧、抗血栓、抗糖尿病、抗菌、解熱など様々な薬理効果が見出されている。このような背景からインドロキノリンアルカロイドは、格好の合成標的となっており、これまで数多くの合成例が報告されている。3) Cryptolepine (1)の全合成に関してみると、その経路はquindoline (2)を形成後、N-メチル化することで1へと導いており、いかにしてquindolineを構築するかに重点が置かれている。
我々は、cryptolepineをインドールパーツとアニリンパーツとに分け、これらを組み合わせた後に環化する合成経路を想定した。そして、この縮合を可能にするインドールパーツとして、これまで有機合成に利用されていないインドール-2,3-エポキシドを設定した。本研究では不安定なエポキシド等価体の開発と反応性を確立し、その反応性を利用してcryptolepine (1)の全合成を達成することを目的としている。


【逆合成解析】
Cryptolepine (1)は、インドロ[3,2-b]キノリン骨格とその5位窒素上にメチル基を有する。我々は、3-アミノインドール体9bの2位ホルミル化と続く環化によりキノリン環を形成して1を合成できると考えた（Scheme 1）。インドール9bは2-ヒドロ

DOI： 10.24496/tennenyuki.60.0_583-588

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：英語   出版者・発行元：Japan Institute of Heterocyclic Chemistry  

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記述言語：日本語   出版者・発行元：天然有機化合物討論会実行委員会  

DOI： 10.24496/tennenyuki.59.0_405

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記述言語：日本語   出版者・発行元：福山大学薬学部  

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記述言語：日本語   出版者・発行元：天然有機化合物討論会実行委員会  

<p>1. 序論</p><p> 近年、インドロ[2,1-b]キナゾリンを基本骨格とするアルカロイド群がPhaius mishmensis (Orchidaceae)¹⁾、Isatis indigotica (Cruciferae)²⁾、や Cephalantheropsis gracilis(Orchidaceae)³⁾から相次いで見出されている (図1)。Phaitanthrin D (6)とラセミ体として単離されたcruciferane (8)を除き、絶対立体配置はX線結晶構造解析により決定された。また2014年、中国伝統薬物成分として知られるtryptanthrin (1a)の8位メチル体1bに、胚性腫瘍 (Embryonal Carcinoma) 細胞から心筋様細胞 (cardiomyocyte-like cell)への分化促進作用を有することが報告された⁴⁾。インドロ[2,1-b]キナゾリン骨格を有する特異な構造とともに多彩な生物活性を示すことから、新規合成法の開発や生物活性について大きな関心を集めている⁵⁾。</p><p> これらインドロ[2,1-b]キナゾリンアルカロイド1-9の合成では、キナゾリン骨格の構築が鍵となる。今回我々は、インドロ[2,1-b]キナゾリン簡便合成法の開発とその応用性の検討を行い、6を除くインドロ[2,1-b]キナゾリンアルカロイドの全合成を達成した。本討論会では合成の経緯と詳細について報告する。</p><p>2.合成計画</p><p> 我々の合成計画をScheme 1に示す。まず、インドール-3-カルバルデヒド (10a) および スカトール (11a)の酸化反応により生じるホルメート12aの酸化的二量化反応によるtryptanthrin (1a) のワンポット合成を計画した (式1)。Phaitanthrin A (3), B (4)、cruciferane (8)とcephalanthrin A (9) は 合成した1aから変換することとした。また、イサト酸無水物 (13a)と10bの酸化的縮合によりインドロ[2,1-b]キナゾリン骨格が構築出来れば、phaitanthrin C (5) へ変換できると考えた (式2)。</p><p>Phaitanthrin E (7) はインドールカルボン酸メチルエステル (15)とイサト酸無水物 (13a)の縮合/C-Hアミノ化反応によりワンポットで合成できると期待した (式3)。</p><p> これら合成計画の特徴として、1) ワンポットもしくは短工程であること、2) 出発原料が安価に市販されているため各種誘導体合成に適していることが挙げられる。</p><p>3.酸化的二量化反応によるインドロキナゾリン1の合成 </p><p> これまでに我々は、複素環アルデヒドのDakin酸化によるキノンのワンポット構築法を鍵反応の一つとする抗腫瘍性抗生物質calothrixin AとBの全合成を報告している⁶⁾。全合成の検討途上において、Dakin酸化のモデル基質としてインドール-3-カルバルデヒド (10a) を用い検討したところ、偶然にもtryptanthrin (1a) がワンポット反応操作で得られた (スキーム 2)。この発見を契機として、1aの簡便合成法の開発研究に着手した。まず、アルデヒド10aを基質として用いDakin酸化を検討した (表1)。酸化剤としてmCPBAを用いた場合、収率5%で１aを得た。過酸化水素を用いた反応において目的物を得ることはできなかったが、触媒量の(PhSe)₂を加えると収率が向上した。さらに検討した結果、過酸化尿素を用いると収率55%で1aが得られることを見出した。さらに、置換基を持つアルデヒド10のDakin酸化を検討した結果、種々の置換基R¹を持つ1を得た⁷⁾。</p><p>(View PDFfor the rest of the abstract.)</p>

DOI： 10.24496/tennenyuki.58.0_Poster11

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記述言語：英語   出版者・発行元：福山大学薬学部  

9,10-Phenanthrenequinone (9,10-PQ) is one of the most abundant quinones among diesel exhaust particulates. Recent data have suggested that quinones induce apoptosis in immune, epithelial and tumor cells, leading to respirator illness; however, the mechanisms by which quinones induce apoptosis and the structure required for this remain unknown. We studied the antitumor activity of 9,10-PQ analogs against two human tumor cell lines, HCT-116 colon tumor cells and HL-60 promyelocytic leukemia cells. The loss of the cis-orthoquinone unit in 9,10-PQ abrogated its ability to induce apoptosis in the two tumor cell lines, and the LC50 values of these analogs were indicated over 10 μM. An analog of 9,10-PQ in which the biaryl unit had been deleted displayed a reduced ability to induce tumor cell apoptosis, while the analogs 1,10-phenanthroline-5,6-dione (9) and pyrene-4,5-dione (10), which also had modified biaryl units, exhibited increased tumor cell apoptotic activity. The cis-orthoquinone unit in 9,10-PQ was identified as essential for its ability to induce apoptosis in tumor cells, and its biaryl unit is also considered to influence orthoquinone-mediated apoptotic activity.9,10-Phenanthrenequinone (9,10-PQ) is one of the most abundant quinones among diesel exhaust particulates. Recent data have suggested that quinones induce apoptosis in immune, epithelial and tumor cells, leading to respirator illness; however, the mechanisms by which quinones induce apoptosis and the structure required for this remain unknown. We studied the antitumor activity of 9,10-PQ analogs against two human tumor cell lines, HCT-116 colon tumor cells and HL-60 promyelocytic leukemia cells. The loss of the cis-orthoquinone unit in 9,10-PQ abrogated its ability to induce apoptosis in the two tumor cell lines, and the LC50 values of these analogs were indicated over 10 μM. An analog of 9,10-PQ in which the biaryl unit had been deleted displayed a reduced ability to induce tumor cell apoptosis, while the analogs 1,10-phenanthroline-5,6-dione (9) and pyrene-4,5-dione (10), which also had modified biaryl units, exhibited increased tumor cell apoptotic activity. The cis-orthoquinone unit in 9,10-PQ was identified as essential for its ability to induce apoptosis in tumor cells, and its biaryl unit is also considered to influence orthoquinone-mediated apoptotic activity.

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記述言語：英語   出版者・発行元：福山大学薬学部  

A one-pot approach to 3,3'-bisindolylmethane derivatives from nitrobenzene derivatives through the Bartoli indole synthesis was developed, in which the acid used to quench the reaction markedly affected its outcome. Quenching the reaction with concd HCl produced 3,3'-bisindolylmethane in contrast to the formation of 7-substituted indole by quenching with NH4Cl.A one-pot approach to 3,3'-bisindolylmethane derivatives from nitrobenzene derivatives through the Bartoli indole synthesis was developed, in which the acid used to quench the reaction markedly affected its outcome. Quenching the reaction with concd HCl produced 3,3'-bisindolylmethane in contrast to the formation of 7-substituted indole by quenching with NH4Cl.

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記述言語：英語   出版者・発行元：福山大学  

Covering: 2010-2011. Previous review: Nat. Prod. Rep. 2010, 27, 1630-1680This review covers the literature on simple indole alkaloids and those with a non-rearranged monoterpenoid unit from the beginning of 2010 up to the end of 2011, which includes newly isolated alkaloids, structure determinations, total syntheses and biological activities.Covering: 2010-2011. Previous review: Nat. Prod. Rep. 2010, 27, 1630-1680This review covers the literature on simple indole alkaloids and those with a non-rearranged monoterpenoid unit from the beginning of 2010 up to the end of 2011, which includes newly isolated alkaloids, structure determinations, total syntheses and biological activities.

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記述言語：日本語   出版者・発行元：(公社)日本薬学会  

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記述言語：日本語   出版者・発行元：天然有機化合物討論会実行委員会  

<p>1.序論</p><p> 1959年にOchrosia elliptica Labill (Apocynaceae)から単離されたellipticine (1) は抗腫瘍活性を有するピリドカルバゾールアルカロイドであり、現在まで数多くの植物中に見出されている (Figure 1)¹⁾。顕著な抗腫瘍活性を示すことから、誘導体・類縁天然物を含めて多数の合成法が開発され、それらの抗腫瘍活性についての検討が現在も続けられている²⁾。</p><p> Calothrixin A (2)、B (3) は1999年に藍色細菌cyanobacteria Calothrix属からRichardらのグループにより単離構造決定された^３⁾。 ピリドカルバゾールにベンゼン環が縮環したインドロフェナンスリジン骨格を有する特異な構造とともに、強い抗腫瘍活性や抗マラリア活性を示すことから、合成法の開発および生物活性評価について大きな関心を集めている⁴⁾。これら縮環型カルバゾールアルカロイド1、2、3の合成では、含窒素多環性骨格の構築が鍵となる。</p><p> 多環性骨格を有する天然物の合成における鍵反応としてトリエンの6p-電子環状反応の利用はよく知られている。一般的に、加熱条件での反応、または光照射を用いて環化反応が行われている⁵⁾。他のペリ環状反応とは異なりルイス酸を用いる触媒的6p-電子環状反応の報告は極めて限られ、一般的な反応となっていない⁶⁾。今回、触媒的6p-電子環状反応の開発とその応用性の検討を行い、ピリドカルバゾールアルカロイドとインドロフェナンスリジンアルカロイドの全合成を達成したので報告する。</p><p>2.合成計画</p><p> 我々の合成計画をScheme 1に示す。系中でインドールより調製したインドリルボレート4とビニルブロミド5とのタンデムクロスカップリング反応によるトリエン6の構築⁷⁾、さらにはトリエン6の6p-電子環状反応による多環性化合物7の構築を鍵段階とする1、2、3の合成を計画した。この合成計画の特徴は、1) トリエン6が共通原料であるので原料供給が容易なこと、2) 同じ鍵反応を用い異なる骨格の天然物や誘導体を合成できることが挙げられる。</p><p>3.6p-電子環状反応の検討 </p><p> 我々は先に、インドリルボレート4を用いるellipticine (1)の合成を報告しているが⁸⁾、トリエンの環化によるピリドカルバゾール環の構築に難を残している。そこでまず、全合成に先立ち、トリエン6の環化反応について金属錯体をルイス酸とする6p-電子環状反応の開発を検討した (Table 1)。 この結果、これまで全く報告例のない (CuOTf)₂•toluene錯体を用いる6p-電子環状反応の開発を行うことができ, さらに触媒的環化反応への適用も可能であることがわかった (entries 1-4)。さらに反応条件の検討を行い、トリエン6を(CuOTf)₂•toluene錯体 (0.1 当量) およびPCC (1.2 当量)とともに塩化メチレンーアセトニトリル混合溶媒中、室温で3時間攪拌することにより環化体7を高収率で得ることができた (entry 5)。(CuOTf)₂•benzene錯体を用いても同様の収率で環化体を得ることができたが、Cu(OTf)₂を用いると収率が低下した(entries 6-8)。</p><p> 光照射やルイス酸を用いる反応において、N-BocとN-OMeを有するトリエン</p><p>(View PDFfor the rest of the abstract.)</p>

DOI： 10.24496/tennenyuki.56.0_Poster4

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

We have demonstrated a new approach to synthesizing calothrixins A and B through the palladium-catalyzed tandem cyclization/cross-coupling reaction of indolylborate by taking advantage of the one-pot generation of the hexatrienes as a key intermediate for constructing indolophenanthridine. In addition, the unprecedented use of CuOTf for 6&pi;-electrocyclization of hexatriene was developed. In another key transformation, indolophenanthridine quinone core of calothrixins was prepared from the indolophenanthridine aldehyde <I>via</I> one-pot Dakin oxidation sequence catalyzed by diphenyldiselenide.

DOI： 10.14895/hannou.37.0.18.0

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

Aryl-substituted 2-azabicyclo[2.2.1]heptanes (aryl-ABH) have significant biological activities. To open the concise entry to aryl-ABH, we have examined metal-catalyzed cross-coupling reaction of arylboronic acids and ABH. When the reaction was carried out with arylboronic acid and ABH in the presence of rhodium/copper combined catalyst under microwave irradiation, diarylated ABH were obtained in one-pot manner. Rhodium complex promoted catalytic addition of arylboronic acids to the double bonds of ABH, and copper complex were essential for the catalytic N-arylation of the amide moiety of ABH.

DOI： 10.14895/hannou.36.0.8.0

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

Pictet-Spengler reaction is one of the most versatile synthetic method in heterocyclic synthesis. Generally, tryptamine derivatives are known to react with aldehydes under acidic or neutral conditions to produce beta-calbolines. On the other hand, we have found that the reaction of Nb-benzylserotonin with aldehydes in the presence of a base proceeded the cyclization to the 4-position of the indole ring, producing azepino[5,4,3-cd]indoles. Therefore, we have investigated the applicability of other aldehydes and serotonin derivatives to the cyclization reaction to devise a novel synthetic route to azepinoindole alkaloids.

DOI： 10.14895/hannou.35.0.55.0

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

The 1,2-differentiated diamination of unactivated alkenes was achieved using dichloramine-T (TsNCl₂ and CH₃CN as nitrogen sources in the presence of a catalytic amount of copper(II) complex. Various alkenes and nitriles could be applicable for the diamination, in which the cis-selectivities were observed in all cases. However, a few substrates gave poor yields mainly due to the formation of haloamine side product which would arised from ring-opening of the aziridinium intermediates by Cl^- in an S_N2 manner instead of CH₃CN. In these cases, the enhanced formation of diamine was observed when the reaction was performed at -20 C. The methodology described herein allows rapid access to cis-vicinal diamines.

DOI： 10.14895/hannou.34.0.8.0

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

The arylation of 2-azabicyclo[2.2.1]hept-5-en-3-ones (ABH) with arylboronic acids was achieved using a catalytic amount of a rhodium(I) complex under microwave irradiation, in which the ring-opening of ABH and the multiple alkylation did not occur. The remote substituents effects on the chemical yields and the regioselectivities (syn : anti = 56 : 44 to 85 : 15) were observed. On the other hand, the reaction under the conventional conditions was sluggish in all cases. Using copper(II) complex, addition of arylboronic acids to N-H ABH under the conventional conditions afforded N-arylated ABH in good yield. In this case, the microwave irradiation was also found to promote the arylation of ABH, improving the rates and yields of these reactions.

DOI： 10.14895/hannou.33.0.54.0

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記述言語：日本語   出版者・発行元：日本薬学会化学系薬学部会  

A recent study from our laboratory has shown that Rh₂(S-TCPTTL)₄, characterized by substitution of chlorine atoms for four hydrogen atoms on the phthalimido group in the parent Rh(II) complex, is well suited for enantioselective C&ndash;H amidation reation with [(4-nitrophenyl)sulfonylimino]phenyliodinane. As a logical extension of our study in this area, we addressed the enantioselective amidation of silyl enol ethers catalyzed by chiral Rh(II) carboxylates. The Rh(II)-catalyzed aziridination of acyclic silyl enol ethers with [(2-nitrophenyl)sulfonylimino]phenyliodinane followed by treatment with aq. TFA afforded optically active &alpha;-amino ketones. The fluorinated catalyst, Rh₂(S-TFPTTL)₄, proved to be the catalyst of choice for this process, exhibiting the highest enantioselectivity of 95% ee. The effectiveness of the present catalytic method has been demonstrated by the enantioselective synthesis of (&ndash;)-metazocine.

DOI： 10.14895/hannou.32.0.28.0

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