Authorship：Lead author,　Last author,　Corresponding author   Publishing type：Research paper (scientific journal)  

DOI： 10.3390/chemistry6040034

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<jats:p>Herein, we introduce a new synthetic protocol using 2-aminobenzoyl surrogates, allowing concise entry to decorated 2-aminobenzoyl derivatives in the absence of transition metals, acid chlorides, and specific reagents.</jats:p>

DOI： 10.1039/d4ob01218f

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Authorship：Last author,　Corresponding author   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/acs.joc.4c00884

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<jats:p>The switchable synthesis of 3-aminoindolines and 2’-aminoaryl acetic acids from the same substrates, 3-azido-2-hydroxyindolines, was developed through denitogenative electrophilic amination of Grignard reagents. The key to success is the serendipitous...</jats:p>

DOI： 10.1039/d4cc01448k

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<jats:p>Natural products having a C3–N1′ bisindole framework are unique structures with potential axial chirality. This minireview summarizes the recent progress of the methodology for constructing C3–N1′ bisindoles along with the possible mechanism.</jats:p>

DOI： 10.1039/d3ob02089d

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DOI： 10.1002/ejoc.202301130

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DOI： 10.3390/chemistry5040177

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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

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DOI： 10.1021/acs.joc.3c00691

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DOI： 10.1021/acs.joc.3c00013

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Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：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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DOI： 10.3390/IJMS24054411

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DOI： 10.1021/acs.joc.2c02561

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DOI： 10.1039/D3RA90053C

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(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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DOI： 10.1021/acs.jnatprod.2c00559

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Organic &amp; Biomolecular Chemistry  

DOI： 10.1039/D2OB90069F

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DOI： 10.1002/chem.202201113

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DOI： 10.1021/acs.orglett.2c00370

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DOI： 10.1039/D2QO00048B

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Use of 3-azidoindoles in organic synthesis remains difficult task owing to their instabilities. Herein, we report a general and concise approach for tackling this problem by using 3-azidoindole surrogates. The...

DOI： 10.1039/d1cc06033c

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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

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DOI： 10.1039/d0cc04795c

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Authorship：Last author,　Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.14894/faruawpsj.56.8_757

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<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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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

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DOI： 10.1039/D0CC01210F

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DOI： 10.3987/com-19-s(f)19

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Authorship：Lead author,　Corresponding author   Language：Japanese   Publisher：The Society of Synthetic Organic Chemistry, Japan  

<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

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DOI： 10.1039/d0ob01038c

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DOI： 10.1039/D0OB01038C

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DOI： 10.1055/s-0039-1690734

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DOI： 10.1002/hlca.201900116

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DOI： 10.3987/com-19-14077

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DOI： 10.1021/acs.orglett.9b01108

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DOI： 10.1021/acs.orglett.8b04120

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<p>The regioselective synthesis of pyrano[3,2-<italic>e</italic>]indole alkaloid fontanesine B have been accomplished by C4 Pictet–Spengler cyclization and Bischler–Napieralski-type cyclization of a trichloromethyl carbamate.</p>

DOI： 10.1039/C9RA02321F

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DOI： 10.3987/com-18-s(f)30

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DOI： 10.1021/acs.orglett.8b00332

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DOI： 10.1021/acs.orglett.8b00330

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DOI： 10.1002/hlca.201700284

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DOI： 10.3987/COM-18-13866

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<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

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DOI： 10.3987/com-17-s(t)15

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DOI： 10.1039/c7qo00549k

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DOI： 10.1055/s-0036-1588438

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DOI： 10.1021/acs.orglett.7b01940

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DOI： 10.1039/c7cc01406f

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DOI： 10.1021/acs.jnatprod.7b00008

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DOI： 10.3987/COM-16-S(S)13

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DOI： 10.1021/acs.orglett.6b03466

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DOI： 10.1016/j.ejmech.2016.05.065

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DOI： 10.3987/COM-16-13465

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DOI： 10.1002/ejoc.201600246

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DOI： 10.3987/COM-15-S(T)5

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DOI： 10.5059/yukigoseikyokaishi.74.117

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DOI： 10.3987/COM-15-13228

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DOI： 10.3987/COM-14-S(K)28

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DOI： 10.1039/c5np00032g

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DOI： 10.1007/s00044-014-1061-6

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DOI： 10.1016/j.tetlet.2014.07.113

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DOI： 10.1016/j.tet.2014.01.015

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DOI： 10.3987/COM-13-S(S)31

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DOI： 10.1016/j.bmcl.2013.06.015

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DOI： 10.5059/yukigoseikyokaishi.71.62

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DOI： 10.1021/ol401486s

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DOI： 10.1039/c3np20118j

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DOI： 10.1248/yakushi.12-00233

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DOI： 10.3987/COM-12-S(N)49

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DOI： 10.1002/ejoc.201200657

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DOI： 10.1002/hlca.200890195

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DOI： 10.1016/j.tet.2007.09.003

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DOI： 10.1021/o1702019b

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DOI： 10.1002/adsc.200600591

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DOI： 10.5059/yukigoseikyokaishi.78.637

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Clavicipitic acid (1), aurantioclavine (2), fargesine (3), cimitrypazepine (4),
hyrtiazepine (5), hyerimomine A-C (6-8), hyrtinadines C, D (9, 10) and hyrtioleticulins C, D
(11, 12) are a unique family of indole alkaloids characterized by a novel
azepino[5,4,3-cd]indole ring system. In our continuing interest in the synthesis of indole
alkaloids, we have developed a biomimetic approach by constructing the
azepino[5,4,3-cd]indole in a one-pot manner through the base promoted C-4 Pictet-Spengler reaction of Nb-benzylserotonin (13) or 5-hydroxytryptophan methyl ester (19) with aldehydes. This strategy allowed the synthesis of common key structures of azepinoindole
families.
A concise synthesis of aurantioclavine (5) was accomplished in only three steps from
Nb-benzylserotonin (13) and aldehyde 20 by using this strategy. The reaction of 13 with 20
in the presence of Et₃N in MeOH, followed by treatment with Tf₂O provided azepinoindole 29 in 60% yield. Subsquentry, conversion of 29 to 2 was achived via catalytic reduction.
Recentry, we reported the first synthesis of the azepinoindole alkaloid hyrtioreticulins
C and D (11, 12) through a C-4 Pictet-Spengler reaction between 5-hydroxytryptophan
methyl ester (19) and acetaldehyde (21). The C-4 Pictet-Spengler reaction using DIEA in
MeOH was carried out under microwave irradiation, and allowed to give trans-25a and
cis-25b in 59% and 4% yield, respectively. The methyl esters 25 were subjected to
hydrolysis and gave hyrtioreticulins C and D (11, 12) in 70-72% yield.
On the other hand, the reaction of 19 with indole-3-carbaldehyde 22 was successful in
the presence of DABCO in TFE, leading to 26 in 85% yield. The removal of Ts and Bn
group were performed by Mg/MeOH and H₂/Pd-C provided 32 in 50%. Further
transformation to 5 was failed due to instability of 32 under oxidation conditions.
Further studies directed to the synthesis of other azepinoindole alkaloids with the use of
base-promoted C-4 Pictet-Spengler reaction are in progress.

DOI： 10.24496/tennenyuki.59.0_405

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<p> Tryptanthrin (1a), a indolo[2,1-b]quinazoline alkaloid with a potent antitumor activity, was isolated from the culture of fungus Candida lipolytica. Several related alkaloids, such as candidine (2), phaitanthrins A (3), B (4), C (5), D (6), E (7), cruciferane (8), and cephalanthrin A (9) have also been found in a wide range of natural sources. Because their diverse biological activities and structural intricacy, these alkaloids have been the target numerous synthetic studies. We envisaged oxidative dimerization of indoles for the construction of these indolo[2,1-b]quinazoline. Herein, we describe the total synthesis of indolo[2,1-b]quinazoline alkaloids tryptanthrin (1a), candidine (2), phaitanthrins A (3), B (4), C (5), E (7), cruciferane (8), and cephalanthrin A (9) using oxidative dimerization of indoles or amination/condensateion cascade as the key step.</p><p> After intensive investigations, we found that urea hydrogen peroxide (UHP) prompted dimerization of indole-3-carbaldehyde (10a) to tryptanthrin (1a) in good yields, while other oxidants did not cause this dimerization at all. In addition, oxidative dimerization of skatole (11a) via C-H oxidation, afforded 1a, could proceed in the presence of CuI and PCC. </p><p> Next, the conversion of 1a to phaitanthrins A (3), B (4), C (5) cruciferane (8), and cephalanthrin A (9) could be carried out. In the course of their synthesis, the unprecedented one-pot formation of candidine (2) via trimerization of 10a in the presence of UHP and a catalytic amount of (PhSe)₂ was also observed. </p><p> Phaitanthrin E (7) was also 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. In the key Cu-mediated condensation/amination cascade, a combination of CuI and Et₃N turned out to effect conversion of methyl indole-3-carboxylate (15) to phaitanthrin E (7) in one-pot protocol. Moreover, the acid catalyzed one-pot synthesis of phaitanthrin E (7) via intermolecular aryl C-H amination/intramoecular cyclization cascade using NCS was also developed. </p>

DOI： 10.24496/tennenyuki.58.0_Poster11

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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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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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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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Language：Japanese   Publisher：(公社)日本薬学会  

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<p> Ellipticine (1), a pyridocarbazole alkaloid with a potent antitumor activity, was isolated from Ochrosia elliptica Labill in 1959. Due to its unique structure as well as potent antitumor activity, 1 have attracted much attention in chemical and biological communities. The structurally-related alkaloids calothrixin A (2) and B (3), a potent antitumor antibiotics, were isolated from cyanobacteria Calothrixin 1999. These alkaloids are characterized by the fused polycyclic ring systems including carbazole. Although there have been reported 6p-electrocyclization that allow concise construction of carbazole core, there was no precedent for construction of carbazoles by catalytic 6p-electrocyclization. We envisaged catalytic 6p-electrocyclization of triene containing indole for the construction of these carbazole core. Herein, we describe the total synthesis of antitumor indole alkaloids based on the Pd-catalyzed tandem cross-coupling/cyclization and Cu-catalyzed 6p-electrocyclization of trienes. </p><p> The triene 6 were readily synthesized from indolylborate 4 and enyne 5 by Pd-catalyzed tandem cross-coupling/cyclization in one-pot protocol. After intensive investigations, we found that (CuOTf)₂•toluene complexes prompted cyclization of 6 to carbazole 7 in good yields, while other Lewis acids and metal complexes did not cause this cyclization at all. In addition, this Cu-promoted cyclization could proceed in the presence of catalytic amount of (CuOTf)₂•toluene complexes. This is a first example for 6p-electrocyclization catalyzed by Cu-complexes. Finally, deprotection and oxidation sequeneces of 7 gave ellipticine (1), 9-methoxyellipticine (10), m-alkaloid D (12) and tetrahydroellipticine (13). In the almost same manner, we have completed total synthesis of olivacine (20), guatambuine (22) and janetine (23) as well from carbazole 7d.</p><p> Calothrixin A (2) and B (3) were also synthesized by a convergent methodology that features a concise approach involving the above-mantioned Pd-catalyzed tandem cross-coupling/cyclization, Cu-catalyzed 6p-electrocyclization to construct the carbazole core and Dakin oxidation. In the key Cu-catalyzed 6p-electrocyclization and Dakin oxidation, a combination of Cu(OAc)₂ and PCC turned out to effect conversion of 6b to 26 in one-pot protocol. </p>

DOI： 10.24496/tennenyuki.56.0_Poster4

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Language：Japanese   Publisher：Division of Organic Chemistry, The Pharmaceutical Society of Japan  

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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Language：Japanese   Publisher：Division of Organic Chemistry, The Pharmaceutical Society of Japan  

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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Language：Japanese   Publisher：Division of Organic Chemistry, The Pharmaceutical Society of Japan  

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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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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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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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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