Regular Issue

Vol. 87, No. 6, 2013

13 data found. 1 - 13 listed
Contents | Regular issue | Vol 87, No. 6, 2013
Published online: 27th May, 2013
DOI: 10.3987/Contents-13-87-06
Review | Regular issue | Vol 87, No. 6, 2013, pp. 1209 - 1240
Published online: 14th May, 2013
DOI: 10.3987/REV-13-769

Daiki Kuzuhara and Hiroko Yamada*

*Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0192, Japan


This article reviews the recent reports about the syntheses, structures, photophysical and redox properties of newly synthesized [14]triphyrins(2.1.1), their metal complexes and their core-modified triphyrins, following the overview of the other triphyrin relatives containing three pyrrole rings and more than three methine carbons. Free-base [14]triphyrins(2.1.1) work as tridentate monovalent anionic cyclic ligands and a variety of metal complexes with Re(I), Mn(I), Ru(II), Pd(II), Pd(IV), Fe(II), Fe(III) and B(III) ions were obtained due to the flexible structure of the triphyrin macrocycles. The core-modified [14]triphyrin(2.1.1) was also expected, but the alkoxy-substituted compounds were obtained instead of the desired thiatriphyrin, probably because of the larger size of sulfur atom compared to nitrogen atom and the electronic repulsion between the lone pairs of inner nitrogen atoms.

Full Text HTMLPDF (5.3MB)PDF with Links (5.3MB)
Communication | Regular issue | Vol 87, No. 6, 2013, pp. 1241 - 1247
Published online: 13th May, 2013
DOI: 10.3987/COM-13-12708
Synthesis of Indoles: Sulfur-Assisted Reaction of 2-Nitrostilbenes with Carbon Monoxide

Rui Umeda, Yuuta Nishimoto, Tsukasa Mashino, and Yutaka Nishiyama*

*Faculty of Chemistry and Materials Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan


When 2-nitrostilbenes were treated with carbon monoxide in the presence of elemental sulfur, the reductive N-heterocyclization of the 2-nitrostilbenes smoothly proceeded to give the corresponding indoles in moderate to good yields.

Full Text HTMLPDF (729KB)PDF with Links (729KB)
Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1249 - 1267
Published online: 2nd May, 2013
DOI: 10.3987/COM-13-12669
Dimethyldioxirane Oxidation of N-Substituted-2-methylindoles to Indoxyls and Bisindoxyls

Alberto Aristeo-Dominguez, Myriam Meléndez-Rodríguez,* Oscar R. Suárez Castillo,* Yaneth M. A. Contreras-Martínez, Lizbeth Suárez-Ramírez, Nayely Trejo-Carbajal, Martha S. Morales-Ríos, and Pedro Joseph-Nathan

*Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Mineral de la Reforma, Hidalgo, 42184, Mexico


Oxidation of 2-methylindoles 12a-f with dimethyldioxirane (DMD) revealed that N-unprotected 12b,f and protected N-carbamate 2-methylindole 12c afforded indoxyls 16b,c and o-(N-propionyl)aminobenzoic acid 17f as the main products, while N-alkyl- or N-aryl-2-methylindoles 12a,d,e gave 1,5’-diphenyl-4’,5’-dihydro-3’H-spiro[indole-2,2’-pyrano[3,2-b]indol]-3(1H)-one (10), 2,3'-bisindolin-3-ones 13, dispiro[indole-2,2’-furan-5’,2”-indole]diones 14 or 2-[(3-oxoindolin-2-yl)methyl]-2-hydroxyindolin-3-ones 15. The structure of dimers 10, 13a,d,e, 14a,d and 15a,d followed from NMR measurements, X-ray diffraction analysis confirmed those structures of 13a,d,e, 14a,d and 15d, and some mechanistic implications are discussed.

Full Text HTMLPDF (1.8MB)PDF with Links (1.8MB)
Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1269 - 1278
Published online: 10th May, 2013
DOI: 10.3987/COM-13-12714
Development of a Novel Method for Warfarin Synthesis via Lipase-Catalyzed Steroselective Michael Reaction

Kaoru Sano, Shun-ichi Saito, Yoshihiko Hirose, Yoshihito Kohari, Hiroto Nakano, Chigusa Seki, Michio Tokiwa, Mitsuhiro Takeshita, and Koji Uwai*

*Department of Applied Sciences, Graduate School of Engineering, Muroran Institute of Technology, 27-1 Mizumoto, Muroran, Hokkaido 050-8585, Japan


Steroselective synthesis of warfarin by promiscuous lipase-catalyzed Michael addition of 4-hydroxycoumarin and benzylideneacetone has been developed. The best result was obtained using lipase AS as a catalyst in anhydrous dimethylsulfoxide (DMSO) with 1:3 molar ratio of 4-hydroxycoumarin to benzylideneacetone at 20ºC for 7 d. The yield and enantiomeric excess were 85% and 45%ee (R-form), respectively.

Full Text HTMLPDF (841KB)PDF with Links (841KB)
Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1279 - 1287
Published online: 10th May, 2013
DOI: 10.3987/COM-13-12720
Synthesis of 5-Amino or 4-Amino Substituted 7-Aza-isoindolin-1-ones

Heng Zhou, Qunfeng Shi, Xiangchao Liu, Xiaoping Zhan, Zenglu Liu, and Zhenmin Mao*

*School of Pharmacy, Shanghai Jiaotong University , No.800 Dongchuan Road, Minhang District, Shanghai 200240, China


A simple and convenient route for the synthesis of a series of 5-amino or 4-amino substituted 7-aza-isoindolin-1-ones is described. Amino substituted pyridine derivatives were cyclized with different amines in alkaline condition to give the desired products.

Full Text HTMLPDF (749KB)PDF with Links (749KB)
Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1289 - 1299
Published online: 2nd May, 2013
DOI: 10.3987/COM-13-12721
Thermal and Photochemical Rearrangements of 3-Arylamino-2-phenyl-1H-inden-1-ones to N-Arylphthalimides

Masayuki Kawai, Eriko Sakanoshita, Motoko Akita, and Keiji Kobayashi*

*Department of Chemistry, Faculty of Science, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan


Upon heating to above their melting temperatures, 3-arylamino-2-phenyl-1H-inden-1-ones and 2,2’-diphenyl-3,3’-bis(arylimino)- [2,2’-bi-1H-indene]-1,1’-dione undergo a skeletal rearrangement to afford N-arylphthalimides along with benzoic acid in the presence of atmospheric oxygen. The photoreaction of these compounds in acetonitrile also results in the formation of these products. The mechanism of these reactions, including the formation of a peroxyl radical followed by its conversion to a nitrogen-centered radical, is proposed.

Full Text HTMLPDF (1.2MB)PDF with Links (1.2MB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1301 - 1309
Published online: 16th April, 2013
DOI: 10.3987/COM-13-12695
Unexpected Behaviour of 6-Cyanopurines Towards Secondary Amines

Amal Al-Azmi* and K. Anita Kumari

*Department of Chemistry, Faculty of Science, Kuwait University, Safat 13060, Kuwait


Reaction of 6-cyanopurines with excess dimethylamine and excess piperidine at room temperature or by reflux-respectively-yielded a mixture of 6-purinecarboximidamides and N,N-dialkylpurines or piperidin-1-yl(purin-6-yl)methanimine and (piperidin-1-yl)-9H-purine, respectively. 6-Purinecarboximidamides were initially formed from the reaction, whereas N,N-dialkylpurines were detected in the mixture 30 min afterward. Both purines appeared to be generated from different mechanistic pathways.

Full Text HTMLPDF (589KB)PDF with Links (589KB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1311 - 1317
Published online: 8th May, 2013
DOI: 10.3987/COM-13-12701
Synthesis of 2-Sulfanyl-4H-3,1-benzothiazine Derivatives by the Reaction of 2-(Bromomethyl)phenyl Isothiocyanates with Thiols

Kosuke Ezaki, Miyuki Tanmatsu, and Kazuhiro Kobayashi*

*Division of Applied Chemistry, Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, 4-101 Koyama-minami, Tottori 680-8552, Japan


The reaction of 2-(bromomethyl)phenyl isothiocyanates with thiols in the presence of triethylamine gave the corresponding 2-sulfanyl-4H-3,1-benzothiazines. The procedure was successfully applied to the preparation of 1,ω-bis[(4H-3,1-benzothiazin-2-yl)sulfanyl]alkanes using 1,ω-alkanedithiols.

Full Text HTMLPDF (878KB)PDF with Links (878KB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1319 - 1326
Published online: 30th April, 2013
DOI: 10.3987/COM-13-12718
Intramolecular [2π+2π]-Photocyclization and Conformational Preference of 5-(2-Benzo[b]thienyl)-5-ethoxy-5H-dibenzo[a,d]cycloheptene

Motoko Akita, Sin-ya Mohri, Mai Takahashi, and Keiji Kobayashi*

*Department of Chemistry, Faculty of Science, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan


The photoirradiation of 5-(2-benzo[b]thienyl)-5-ethoxy-5H-dibenzo[a.d]cycloheptene (2) in acetonitrile afforded a cagelike tetracyclic compound (1) via intramolecular [2π+2π]-photocycloaddition. The molecular and crystal structures of 1 and 2 were characterized by a single-crystal X-ray diffraction study. The formation of the cycloadduct is discussed in relation to the preferable conformation of the central C-C bond in 2, which was revealed to be in restricted rotation on the basis of the temperature-dependent 1H NMR spectra.

Full Text HTMLPDF (950KB)PDF with Links (950KB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1327 - 1336
Published online: 13th May, 2013
DOI: 10.3987/COM-13-12719
Microwave-Assisted Synthesis of 3-Methyl-1-phenylchromeno[4,3-c]pyrazol-4(1H)-ones under Solvent-Free Conditions

Guo-Yu Yang, Jing-Tian Yang, Cai-Xia Wang, Su-Fang Fan, Pu-Hui Xie, and Cui-Lian Xu*

*College of Science, Henan Agricultural University, Zhengzhou 450002, China


A novel microwave-assisted method for the synthesis of 3-methyl-1-phenylchromeno[4,3-c]pyrazol-4(1H)-ones by the cyclization of 3-[1-(phenylhydrazono)ethyl]chromen-2-ones with CuO/SBA-15 under solvent-free conditions is described. The reaction gave the corresponding chromenopyrazole products in good to excellent yields in short reaction times.

Full Text HTMLPDF (934KB)PDF with Links (934KB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1337 - 1347
Published online: 8th May, 2013
DOI: 10.3987/COM-13-12724
Asymmetric Conversion of (Z)-N-Benzoyl-α-dehydro(9-phenanthryl)alanine -Methylamide into Its Cyclization Intermediates via Photoinduced Electron Transfer

Shin-ichi Matsuki, Takayuki Kimura, Shinsaku Hattori, Kaoru Kawai, Tetsutaro Igarashi, and Tadamitsu Sakurai*

*Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan


Irradiation of (Z)-N-benzoyl-α-dehydro(9-phenanthryl)alanine N´-methylamide [(Z)-1] in 2-propanol-methanol (4:1 v/v) containing (S)-nicotine afforded the (3S,8aS)-3,8a-dihydro-2-dibenzo[f,h]-quinolinone derivative [(3S,8aS)-2] and (3R,8aS)-2 in 20% and 35% enantiomeric excess (ee), respectively. Analysis of the effects of a chiral amine and solvent on the electron transfer-initiated enantioselective photocyclization of (Z)-1 revealed that the magnitude of the ee is predominantly determined by the ability of this amine to form hydrogen bonds at the two sites of the enol intermediate as the precursor of 2.

Full Text HTMLPDF (869KB)PDF with Links (869KB)
Short Paper | Regular issue | Vol 87, No. 6, 2013, pp. 1349 - 1358
Published online: 13th May, 2013
DOI: 10.3987/COM-13-12726

Tetsuro Shimo,* Yuki Taketsugu, Takuya Goto, Masaaki Toyama, Kohji Yoshimura, and Masanori Baba

*Department of Chemistry, Faculty of Engineering, Kagoshima University, Korimoto, Kagoshima 890-0065, Japan


5-Benzyloxy-2-hydroxymethyl-4H-pyran-4-one (2) was synthesized from kojic acid (1) and subsequently reacted with carboxylic anhydride (3a) and a series of carboxylic acid chlorides (3bl) to give the corresponding (5-benzyloxy-4-oxo-4H-pyran-2-yl)methyl carboxylates (4al). These compounds were then reductively debenzylated to afford the (5-hydroxy-4-oxo-4H-pyran-2-yl)methyl carboxylates (5a-l), which were tested for their inhibitory activities against the hepatitis C virus.

Full Text HTMLPDF (831KB)PDF with Links (831KB)
13 data found. 1 - 13 listed