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HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
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Special Issue
Akira Suzuki's Special Issues,Vol. 80, No. 1, 2010
Published online: 16th December, 2009
■ Contents
FREE:PDF (2.5MB)Published online: 16th December, 2009
■ Congratulations on Your 80-Years Birthday to Professor Akira Suzuki
Yurii N. Bubnov*
*A.N.Nesmeyanov Institute of 0rganoelement Compounds, Russian Academy of Sciences, 28 Vavilova str. 119991-GSP-I, V-334, Moscow, Russia
FREE:PDF (703KB)Published online: 16th December, 2009
■ Laudatio Suzuki Akira
Victor Snieckus*
*Department of Chemistry, Queen's University, Kingston, Ontario K6L 3N6, Canada
FREE:PDF (726KB)Published online: 16th December, 2009
■ Curriculum Vitae of Akira Suzuki
*,
FREE:PDF (542KB)Published online: 16th December, 2009
■ Organoboranes in Organic Syntheses Including Suzuki Coupling Reaction
Akira Suzuki*
*3-2-905, Aino-sato 2-Jo, 6-Chome, Kita-ku, Sapporo, 002-8072, Japan
FREE:PDF (2.2MB)Published online: 16th December, 2009
■ List of Publications by Akira Suzuki (1967-2008)
(Only publications concerned with the organoborane chemistry)
*,
FREE:PDF (1.5MB)Published online: 12th March, 2009
■ A New Type of Oxidation-Reduction Condensation by the Combined Use of Phenyl Diphenylphosphinite and Oxidant
Teruaki Mukaiyama,* Kiichi Kuroda, and Yuji Maruyama
*Tokyo Chemical Industry Co., Ltd., 6-15-5 (TCI) Toshima, Kita-ku, Tokyo 114-0003, Japan
Abstract
A new type of oxidation−reduction condensation of alcohols with sulfur, nitrogen, and oxygen nucleophiles by the combined use of phenyl diphenylphosphinite (PhOPPh2) and oxidants such as azides or diethyl azodicarboxylate (DEAD) are described. In these reactions, chiral secondary and tertiary alcohols are converted into the corresponding chiral sulfides, azides, esters and ethers under mild and neutral conditions with almost complete inversion of stereochemical configuration.
Published online: 2nd July, 2009
■ Pharmaceutical Studies on Vitamin D Derivatives and Practical Syntheses of Six Commercially Available Vitamin D Derivatives That Contribute to Current Clinical Practice
Noboru Kubodera*
*Chugai Pharmaceutical Company, Ltd., 2-1-1, Nihonbashi-Muromachi, Chuo-ku, Tokyo 103-8324, Japan
Abstract
Three milestones exist in vitamin D research from the perspective of pharmaceutical development. The article first discusses the various milestones outlining vitamin D and derivatives in terms of pharmaceutical applications. Several active vitamin D derivatives based on the findings during the third milestone are now commercially available and contributing to current clinical practice. The paper also reviews the practical syntheses of six derivatives, maxacalcitol, calcipotriol, tacalcitol, paricalcitol, doxercalciferol, and falecalcitriol, as well as summarizes future prospects for further drug development.
Published online: 9th March, 2009
■ Efforts toward the Synthesis of Pseudolaric Acid A: Intramolecular Bromoetherification as a Multipurpose Synthetic Tool
Jeremy D. Pettigrew and Leo A. Paquette*
*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.
Abstract
Regioselective double bond cleavage within 5, required for access to the trans-fused perhydroazulene framework of pseudolaric acid A (1), has been accomplished via a highly diastereoselective intramolecular bromoetherification process, the latter serving a dual role as a protecting group tactic.
Published online: 9th March, 2009
■ Construction of Fused Thiophene Ring System via Intramolecular CH Arylation by Palladium Catalysis
Atsunori Mori,* Nobumichi Arai, Tomomi Hatta, and Daiki Monguchi
*Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
Abstract
Intramolecular CH arylation of a thiophene derivative in the presence of a palladium catalyst furnishes fused tricyclic thiophene in a high yield. The obtained thiophene undergoes further intermolecular CH arylation with a palladium catalyst and AgNO3/KF.
Published online: 11th May, 2009
■ Solid Guests in Reversible Encapsulation Hosts
Dariush Ajami, and Julius Rebek, Jr.*
*Department of Chemistry, The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, U.S.A.
Abstract
The space inside a cylindrical capsule host is probed with a series of adamantane guests. The results indicate that higher packing coefficients are possible for solid guests than for liquids or gases in encapsulation complexes.
Published online: 12th May, 2009
■ Mild and Selective O-Glycosylations of Primary Alcohols with the Thioglucosaminide Derivative Promoted by N-Iodosuccinimide and HBF4-Adosrobed on Silica Gel
Michio Kurosu* and Kai Li
*Department of Microbiology, Immunology and Pathology, College of Veterinary Medicine and Biomedical Sciences, Colorado State University, 1682 Campus Delivery, Fort Colllins, CO 80523-1682, U.S.A.
Abstract
Selective glycosylations of primary alcohols with the thioglucosaminide 1 are achieved by using NIS and HBF4-SiO2. HBF4-SiO2 is a mild Brønsted acid which requires primary alcohols or phenols to effectively activate 1 with NIS at rt. A wide range of functional groups are tolerated under these conditions.
Published online: 13th July, 2009
■ Stereoselective Synthesis of α-Methylene-γ-butyrolactams from Ethyl 2-(Bromomethyl)acrylate and Chiral Sulfinyl Aldimines Mediated by Indium
Haythem K. Dema, Francisco Foubelo,* and Miguel Yus*
*Department of Organic Chemistry, Faculty of Sciences and Institute of Organic Synthesis (ISO), University of Alicante, P.O. Box 99, 03080 Alicante, Spain
Abstract
The reaction of ethyl 2-(bromomethyl)acrylate (1) with chiral N-tert-butylsulfinyl aldimines 2 and indium powder in THF at 100 ºC for 48 h affords, after hydrolysis, a mixture of N-tert-butylsulfinyl aminoesters 3 and α-methylene-γ-butyrolactams 4. From the reaction mixture, compounds 3 were quantitatively converted to the expected butyrolactams 4 after removal of the tert-butylsulfinyl group under acidic conditions and final basic workup. The whole process takes place in high overall yields and with fairly good stereoselectivities.
Published online: 16th June, 2009
■ A New Entry for Preparation of 2-Substituted Azaindoles
Montaser Shaykoon Ahmed Shaykoon, Fuyuhiko Inagaki, and Chisato Mukai*
*Division of Pharmaceutical Sciecnes, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract
A series of 2-substituted 5-, 6- and 7-azaindoles were synthesized from iodo-N-(tert-butoxycarbonyl)aminopyridines via the corresponding allenyl derivatives.
Published online: 17th July, 2009
■ Asymmetric Hydrogenation of Aromatic Heterocyclic Ketones Catalyzed by the MsDPEN–Cp*Ir(III) Complex
Noriyuki Utsumi, Kunihiko Tsutsumi, Masahiko Watanabe, Kunihiko Murata, Noriyoshi Arai, Nobuhito Kurono, and Takeshi Ohkuma*
*Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0828, , Japan
Abstract
Asymmetric hydrogenation of aromatic heterocyclic ketones catalyzed by Cp*Ir(OTf)(Msdpen) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the heterocyclic alcohols in 93% to >99% ee. The reaction is conducted in a methanolic solution with a substrate-to-catalyst molar ratio of 200–5000 under 15 atm of H2. The heterocyclic rings of substrates are left intact.
Published online: 21st July, 2009
■ Phenanthrene-4,5-diylbis(10-methylacridinium) with a Short C+ - - C+ Contact: Preparation, Molecular Structure, Redox Properties, and Electrochromic Interconversion with Dihydropyrene Derivative
Takanori Suzuki,* Yasuyo Yoshimoto, Kazuhisa Wada, Takashi Takeda, Hidetoshi Kawai, and Kenshu Fujiwara
*Division of Chemistry, Graduate School of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
Abstract
The title dication (12+) was generated by oxidative bond cleavage of a 4,5-dihydoropyrene derivative (2) with two spiro(10-methylacridan) units. Despite the skewed deformation of the arylene spacer, two cationic chromophores in 12+ are forced to face in a proximity with a very short interatomic separation of 2.98(1) Å between carbenium centers (X-ray), which makes the LUMO level of 1 much lower than that of biphenyl-2,2'-diyl-type dication (32+).
Published online: 18th August, 2009
■ Highly Active Rhodium Catalyst with Electron-Poor Diphosphine Enables Efficient Synthesis of Chiral 4-Aryl-δ-lactones
Toshinobu Korenaga,* Ryota Maenishi, Kazutaka Osaki, and Takashi Sakai*
*Department of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Chiral 4-aryl-δ-lactones could be synthesized efficiently with high enantioselectivity through asymmetric 1,4-addition of arylboronic acid to α,β-unsaturated lactones using Rh catalyst including electron-poor diphosphine (MeO-F12-BIPHEP) at room temperature for 1 h. In particular, our catalytic system proved to be applicable to relatively large coumarin analogues, giving optically pure 4-phenylchroman-2-one analogues in a short time.
Published online: 31st August, 2009
■ Rhodium-Catalyzed 1,2-Addition of Sb-Phenyl-1,5-azastibocines to Functionalized Aldehydes
Naoki Kakusawa, Shuji Yasuike, and Jyoji Kurita*
*Faculty of Pharmaceutical Sciences, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Simple and efficient addition of a phenyl group to aldehydes was accomplished by the rhodium-catalyzed reaction of Sb-phenyl-1,5-azastibocines. Because of the soft nucleophilic character of 1,5-azastibocines, arylation of functionalized aldehydes having ketone, ester, and halogen moieties can be achieved to afford aryl alcohols. The reaction can be carried out under aerobic conditions, in striking contrast to the reactions with hard nucleophiles such as organolithium and Grignard reagents.
Published online: 6th August, 2009
■ An Effective Kinetic Resolution of Racemic Secondary Benzylic Alcohols Using 3-Pyridinecarboxylic Anhydride and a Chiral Acyl-Transfer Catalyst in the Absence of Tertiary Amine
Kenya Nakata and Isamu Shiina*
*Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
3-Pyridinecarboxylic anhydride (3-PCA) was found to function as an efficient coupling reagent for the kinetic resolution of racemic secondary benzylic alcohols with achiral carboxylic acids in the presence of a catalytic amount of (+)-BTM. A variety of optically active carboxylic esters are produced with high enantiomeric excesses by this new chiral induction system without using a tertiary amine.
Published online: 11th August, 2009
■ Preparation of 2-Sulfonyl-1,2,3-triazoles by Base-Promoted 1,2-Rearrangement of a Sulfonyl Group
Motoshi Yamauchi, Tomoya Miura, and Masahiro Murakami*
*Departmene of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, youdai-katsura, Nishikyo, Kyoto 615-8510, Japan
Abstract
1,2-Rearrangement of a sulfonyl group occurs on treatment of 1-sulfonyl-1,2,3-triazoles with a catalytic amount of 4-dimethylaminopyridine (DMAP) in acetonitrile to give an equilibrium mixture of 1-sulfonyl- and 2-sulfonyl derivatives, with considerable predominance of the latter. Subsequent acidic treatment of the mixture caused selective hydrolysis of the 1-sulfonyl derivative, which led to the isolation of the 2-sulfonyl-1,2,3-triazole in good total yield in a pure form.
Published online: 4th September, 2009
■ Photolytic Preparation of Tetrabromothianthrene and Its Transformation to Dinuclear Phthalocyanines
Takeshi Kimura,* Takeru Obonai, Takayuki Nozaki, Kenji Matsui, Toshiharu Namauo, Akio Yamakawa, and Yutaka Takaguchi
*Center for Instrumental Analysis, Iwate University, 4-3-5 Ueda, Morioka, Iwate 020-8551, Japan
Abstract
Photolysis of dibromobenzotrithiole (1) and tetrabromodibenzo-tetrathiocin (4) in CH2Cl2 produced tetrabromothianthrene (2). Compound (2) was treated with CuCN in DMF at 150 °C to give tetracyanothianthrene (5). Dinuclear phthalocyanine (9) was constructed by treatment of a mixture of 5 and dioctoxyphthalonitrile (6) with lithium in n-pentanol.
Published online: 19th August, 2009
■ Synthesis of Functionalized Chromanes via a Formal [3+3]Cycloaddition of Allene Sulfonamides to Phenols
Ken Hashimoto, Yoshikazu Horino,* and Shigeyasu Kuroda*
*Department of Applied Chemistry, Faculty of Engineering, Toyama University, Gofuku 3190, Toyama 930-8555, Japan
Abstract
The Brønsted acid catalyzed formal [3 + 3] cycloaddition reaction of allene sulfonamides 1 with phenols 2 provides functionalized chromanes. This formal [3 + 3] cycloaddition reaction is proposed to proceed via a stepwise process involving intermolecular hydroarylation followed by intramolecular cyclization.
Published online: 19th August, 2009
■ Substituent Effects on the Electron Transfer-Initiated Photochemical Transformation of 1,2,4-Triazole-substituted α-Dehydroarylalaninamides into 2(1H)-Quinolinone Derivatives
Yuichi Yazawa, Minoru Suzuki, Tetsutaro Igarashi, and Tadamitsu Sakurai*
*Material and Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
An investigation was undertaken to elucidate substituent effects on the photoreactivity of 1,2,4-triazole-substituted α-dehydroarylalaninamides [(Z)-1] as well as on the selectivity of 2(1H)-quinolinone derivatives (2) from a synthetic point of view. It was found that photoinduced electron transfer-initiated cyclization of (Z)-1 bearing a meta-substituted phenyl or a 4-substituted naphthalen-1-yl group in methanol proceeds with a moderate to good efficiency affording the corresponding product 2 in a selectivity ranging from 33 to 100%.
Published online: 20th August, 2009
■ A Hetero Pauson-Khand Reaction of Ketenimines: A New Synthetic Method for γ-Exomethylene-α,β-unsaturated γ-Lactams
Takao Saito,* Katsuya Sugizaki, Hiroyuki Osada, Noriki Kutsumura, and Takashi Otani
*Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
A novel ketenimine Pauson–Khand reaction has been described for the first time. C,C,N-Triarylketenimines reacted with alkyne–dicobalthexacarbonyl complexes upon heating in toluene in the presence of dimethyl sulfoxide as a promoter to afford γ-lactams, 5-(diphenylmethylene)-1H-pyrrol-2(5H)-ones, in good yields.
Published online: 21st August, 2009
■ Palladium- or Nickel-Catalyzed Coupling Reaction of Dialkoxyboranes with Chloroarenes: Arylation of 1,3,2-Dioxaborolanes or 1,3,2-Dioxaborinanes
Miki Murata,* Tomoko Sambommatsu, Takeshi Oda, Shinji Watanabe, and Yuzuru Masuda
*Faculty of Engineering Department of Materials Science and Engineering, Kitami Institute of Technology, Koen-cho 165, Kitami, Hokkaido 090-8507, Japan
Abstract
The borylation of electron-deficient aryl chlorides with pinacolborane proceeded in the presence of Bu4NI and a catalytic amount of Pd(dba)2 / bis(2-di-tert-butylphosphinophenyl) ether. The combination of NiCl2(dppp) catalyst and Bu4NBr was also efficient for the borylation of aryl chlorides.
Published online: 19th January, 2009
■ Stereoselective Formal Total Synthesis of Novel Antibiotic (-)-Centrolobine
Debendra K. Mohapatra,* Rita Pal, Hasibur Rahaman, and Mukund K. Gurjar
*Organic Chemistry Division I, Indian Institute of Chemical Technology, Hyderabad-500 007, India
Abstract
A concise and stereoselective formal total synthesis of (−)-centrolobine is achieved utilizing Mioskowski’s Lewis acid mediated epoxide opening followed by ring-closing metathesis as the key reaction.
Published online: 25th February, 2009
■ Enantioselective Total Synthesis of Novel Diterpenoid Pyrones (+)-Sesquicillin and (-)-Nalanthalide from Fungal Fermentations
Takamasa Oguchi, Kazuhiro Watanabe, Hideki Abe, and Tadashi Katoh*
*Department of Synthetic Organic Chemistry, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
We efficiently synthesized (+)-sesquicillin (a glucocorticoid antagonist) and (–)-nalanthalide (a potassium channel Kv1.3 blocker) in a convergent and unified manner starting from (+)-5-methyl-Wieland–Miescher ketone. The synthesis involved the following key steps: (i) a [2,3]-Wittig rearrangement of a stannylmethyl ether to install the stereogenic center at C9 and the exo-methylene functionality at C8 present in the trans-decalin portion, (ii) a coupling reaction of a trans-decalin portion with a γ-pyrone moiety to assemble the requisite whole carbon framework, and (iii) a conversion of a γ-pyrone moiety to an α-pyrone ring to produce (+)-sesquicillin. The present total synthesis has verified the absolute configuration of these natural products.
Published online: 2nd February, 2009
■ Synthesis of 4-Azachromeno[2,3-b]indol-11(6H)-one and Its Derivatives as Analogues of Ellipticine
Yanhong Chen, Chunhao Yang,* and Yuyuan Xie*
*State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, SIBS, Chinese Academy of Science, 555 Zu Chong Zhi Road, Shanghai 201203, China
Abstract
4-Azachromeno[2,3-b]indol-11(6H)-ones (4) and their derivatives (5) as analogues of ellipticine were synthesized through a straightforward, two or three-step process. Tetracyclic heterocycles (4) were obtained by facile cyclization of indolin-2-ones (2) or (3) and 2-chloronicotinoyl chloride under the condition of the ‘Jensen’-reaction. Alkylation of the compounds (4) afforded 6-substituted 4-azachromeno[2,3-b]indol-11(6H)-ones.
Published online: 17th February, 2009
■ Tin-Hydride-Mediated Radical Addition of Alkyl Halides to 2-Methylene-1,3-dithiane Monoxide as a Ketene Equivalent
Suguru Yoshida, Hideki Yorimitsu,* and Koichiro Oshima*
*Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Abstract
Reductive radical addition of alkyl halides to ketene dithioacetal monoxide in the presence of tributyltin hydride and a radical initiator provides the corresponding adducts, 2-alkyl-1,3-dithiane monoxides, in good yields.
Published online: 9th March, 2009
■ Synthesis of 4-Aryl-Substituted Butenolides and Pentenolides by Copper-Catalyzed Hydroarylation
Yoshihiko Yamamoto* and Naohiro Kirai
*Graduate School of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
We have investigated the effect of the type of protecting group used and the tether length of 4- and 5-hydroxy-substituted 2-alkynoates on the yields and selectivity of the product of hydroarylation. The use of methyl, methoxymethyl, and tert-butyldimethylsilyl (TBS) as protecting groups increased the total yield of the products. While the protected 4-hydroxy-2-butynoates afforded products formed from two or more alkyne substrates, 5-hydroxy-2-pentynoate derivatives exclusively yielded 1:1 adducts. These facts suggest that the product selectivity depends on the distance of the alkoxy group from the alkyne moiety rather than the type of the protecting group. Among the protecting groups used in this study, the TBS group was found to produce butenolides and pentenolides in good total yields via the one-pot hydroarylation/lactonization.