HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Teruaki Mukaiyama's Special Issues, Vol. 52, No. 2, 2000
Published online:
■ Fe(III)-Catalyzed Radical Cyclization of Cyclopropanone Thioacetal
Hiroyuki Ohara, Kazutoshi Kubo, Toshiyuki Itoh,* Masaharu Nakamura, and Eiichi Nakamura*
*Department of Chemistry, Faculty of Education, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Oxidative severance of the cyclopropane ring of cyclopropanonethioacetal derivatives caused by treatment of 10 mol% of Ion(III) perchlorate in acetonitrile under air, subsequent cyclization with the olefinic part and reduction by an additional 1,3-dithiane giving cis-fused oxabicyclo[3.3.0]octane-1,1-trimethylenethioacetals in good yield.
Published online:
■ Synthesis of Water Soluble Derivatives of Milbemycin D
Rei Matsueda* and Susumu Higashida
*Exploratory Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Water Soluble 5-O-(S-glutathionylthio)cysteinylmilbemycin D was successfully synthesized by using 3-nitro-2-pyridinesulfenyl (Npys) reagent through esterification of a Boc-cysteine derivative to a hydroxyl group at the C-5 position of milbemycin D, activation of the conventional S-protecting group, and asymmetrical disulfide bond formation.
Published online:
■ Stereoselective C-Glycosylation of 2,3-Dideoxyribofuranosides Controlled by the Methylenephosphonothioate Functional Groups at the 3-Position
Tsutomu Yokomatsu, Tomoyuki Sada, Takanori Shimizu, and Shiroshi Shibuya*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
C-Glycosylation of 2,3-dideoxyribofuranoside (3) having a methylenephosphonothioate functional group at the 3-position with allylic carbonnucleophiles was examined in the presence of a variety of Lewis acids. Good β-selectivity with high chemical yield was observed upon using allyltrimethylsilane as a carbon nucleophile.
Published online:
■ Synthesis of an Enantiomeric 2,5-Di-(E)-propenyltetrahydrofuran-3,4-diol Derivative
Eiju Suzuki, Ken-ichi Takao, and Kin-ichi Tadano*
*Department of Applied Chemistry, Keio University, Hiyoshi, Kohoku-ku Yokohama 223-8522, Japan
Abstract
For total synthesis of a novel bioactive δ-lactone antibiotic FD-211, a key intermediate, a 2,5-di-(E)-propenyltetrahydrofuran-3,4-diol derivative, was synthesized from diacetone D-glucose.
Published online:
■ Enantioselective Synthesis of (+)-Decarestrictine L from (2E,5E)-Dibenzyloxy-2,5-heptadien-4-ol
Tomoyuki Esumi, Rieko Kimura, Masako Mori, Yoshiharu Iwabuchi, Hiroshi Irie, and Susumi Hatakeyama*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
(+)-Decarestrictine L has been synthesized in enantiomerically pure form from (3R,4S)-1-benzyloxy-6-heptene-3,4-diol, prepared from (2E,5E)-1,7-dibenzyloxy-2,5-heptadien-4-ol, employing either Me2AlCl promoted methylative cleavage of (1R,5R,6S)-6-benzyloxy-2,9-dioxabicyclo[3.3.1]nonane or DIBAH promoted reductive cleavage of (1R,5R,6S)-6-benzyloxy-1-methyl-2,9-dioxabicyclo[3.3.1]nonane for the construction of the substituted pyran ring system.
Published online:
■ Lewis Acid Promoted [4+2] Annulation of Allylsilane and Allylgermane with Aldimine; Preparation of Tetrahydroquinolines
Takahiko Akiyama,* Megumi Suzuki, and Hirotaka Kagoshima
*Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1, Mejiro, Toshima-ku, Tokyo 171-8588, Japan
Abstract
On treatment of aldimines derived from aromatic aldehydes and aniline with allylsilane in the presence of Lewis acid, [4+2] cycloannulation took place smoothly to afford tetrahydroquinoline derivatives in moderate to good yields.
Published online:
■ A Novel Simple Method of Synthesis of 2-Amino-4-(-6-)nitroindoles via Base Promoted Condensation of m-Nitroanilines with Nitriles
Nikolai Moskalev and Mieczyslaw Makosza*
*Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland
Abstract
Base promoted condensation of nitrites (RCH2CN) with m-nitroanilines at room temperature results in the formation of 3-alkyl- or 3-aryl-2-amino-4-(-6-) nitroindoles. This multistep process includes presumably nucleophilic substitution of hydrogen (or halogen) in the nitroaromatic ring by the nitrile carbanion and subsequent cyclization of the ortho-aminophenylacetonitriles so formed to give the aminoindoles.
Published online:
■ A New Approach to the Synthesis of Chiral Tetraazacoronands Derived from L-Alanine
Agnieszka Szczepanska, Piotr Salanski, and Janusz Jurczak*
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
Dimethyl α,ω-dicarboxylates react under high pressure or ambient conditions with chiral primary diamino ethers derived from L-alanine to give the chiral cyclic diamides or tetramides in satisfactory yields. The effective preparation of chiral amino components starting from L-alanine is also described.
Published online:
■ Novel Synthesis of Oxadiazinone and Oxadiazepinone Derivatives by Ring Expansion of Diaziridinone
Mitsuo Komatsu,* Norio Sakai, Akira Hakotani, Satoshi Minakata, and Yoshiki Ohshiro
*Faculty of Engineering, Department of Applied Chemistry, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Treatment of N, N'-di-tert-butyldiaziridinone with α-hydroxy ketones in the presence of a catalytic amount of BF3·OEt2 gave carbazate derivatives in excellent yields. Acid-catalyzed recyclization of these compounds easily proceeded to give oxadiazinone derivatives. The reaction was applicable to the synthesis of oxadiazepinone derivatives and also to one-pot process.
Published online:
■ Lanthanoid Triflates Catalyzed Reaction of a Silyl Ynolate with Aldimines
Mitsuru Shindo,* Soichiro Oya, Yusuke Sato, and Kozo Shishido
*Institute for Medicinal Resources, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
A silyl ynolate, prepared from α,α-dibromo ester in one-pot, reacts with N-(p-methoxyphenyl)aldimines in the presence of a catalytic amount of lanthanoid triflates to provide α,β-unsaturated amides with high E selectivity.
Published online:
■ Reaction of Aryl Iodide Derivatives with Homoconjugated Compounds in the Presence of Palladium(II) Acetate to Form Hetero Cyclic Compounds
Toshifumi Takeda and Katsuhiro Saito*
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Reaction of phenol with a tricyclo[3.2.2.02,4]nona—6,9—diene derivative in the presence of palladium(II) acetate afforded a cyclic ether compound, which is considered formally derived from the homo Diels-Alder reaction of the tricyclic compound with phenol followed by dehydrogenation reaction. The yield of the cyclic ether compound was improved by a use of 2-iodophenol instead of phenol. The same type of reaction proceeded between the tricyclic compound and 2-iodoaniline to form a cyclic amine derivative.
Published online:
■ Concise Synthesis of (±)-Brevioxime
Yutaka Nishimura and Takeshi Kitahara*
*Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract
Brevioxime (1) is a juvenile hormone (JH) biosynthesis inhibitor isolated from Penicillium brevicoinpactuin. The synthesis of race mic brevioxime (1) was accomplished in a straightforward manner via the β-ketoamido aldehyde.
Published online:
■ Synthesis of Homochiral β-Sulfinyl Nitrones and Their Application for Enantioselective Synthesis of (+)-Euphococcinine
Shun-Ichi Murahashi,* Jun Sun, Hiroyuki Kurosawa, and Yasushi Imada
*Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
Abstract
Homochiral β-sulfinyl nitrones can be prepared from secondary amines in three steps. Enantioselective synthesis of defensive alkaloid (+)-euphococcinine (9) has been accomplished by means of diastereoselective allylation of homochiral β-sulfinyl nitrone (13) followed by intramolecular 1,3-dipolar cycloaddition reaction.
Published online:
■ Enantioselective Synthesis of Lythraceae Alkaloid Lasubine II via Optically Active 2-Isoxazoline
Yutaka Ukaji,* Masaki Imai, Takehito Yamada, and Katsuhiko Inomata*
*Department of Chemistry, Faculty of Siencce, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract
Enantioselective synthesis of Lythraceae alkaloid lasubine II was achieved via optically active 2-isoxazoline, which was available by the asymmetric 1,3-dipolar cycloaddition of nitrile oxide to an achiral 2-propen-1-ol using diisopropyl (R,R)-tartrate as a chiral auxiliary.
Published online:
■ Difference in Orientation of a Guest within a Cavity of β-Cyclodextrins Bearing an N-Acetylaminoacyl Group
Iwao Suzuki,* Ryoko Onodera, and Jun-ichi Anzai
*Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
1H-NMR studies revealed that either the benzene or the naphthalene ring of 8-anilinonaphthalene-1-sulfonate (ANS) was accommodated by β-cyc1odextrin (β-CyD) bearing an N-Ac-L-Leu residue, while β-CyDs bearing an N-Ac-L-Ile and N-Ac-L-Val residues accommodated the naphthalene ring of ANS.
Published online:
■ Synthesis of Bridged Benzoazabicyclic Compounds Using Radical Translocation/Cyclization Reactions of 1-Alkynyl-2-(o-iodobenzoyl)tetrahydroisoquinolines
Masazumi Ikeda,* Masahiro Hamada, Serry A. A. El Bialy, Katsuaki Matsui, Shimpei Kawakami, Yuka Nakano, Said M. M. Bayomi, and Tatsunori Sato
*Kyoto Pharmaceutical University, Misasagi-Shichonocho, Yamashina, Kyorto 607-8414, Japan
Abstract
Bu3SnH-mediated radical translocation/cyclization reactions of 1-alkynyl-2-(o-iodobenzoyl)tetrahydroisoquinolines were examined. The 1-[3-(trimethylsilyl)prop-2-ynyl]- (10a) and 1-[4-(trimethylsilyl)but-3-ynyl]-1,2,3,4-tetrahydroisoquinoline derivatives (10b), with Bu3SnH in the presence of azobis(isobutyronitrile) in boiling toluene, gave regioselectively the 6,7,8,9-tetrahydro-5H-benzocyclohepten-5,8-imine (12a) and 5,6,7,8,9,10-hexahydrobenzocycloocten-5,9-imine (12b), respectively.
Published online:
■ Efficient Catalytic Procedure for Etherification of Alcohols with MeAl(NTf2)2
Takashi Ooi, Hayato Ichikawa, Yoshifumi Itagaki, and Keiji Maruoka*
*Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
Efficient catalytic etherification of benzyl and allylic alcohols has been accomplished by use of in situ prepared MeAl(NTf2)2 as a catalyst. The new method was also found to be effective for the selective benzylation of allylic alcohols.
Published online:
■ Expedient Stereospecific Synthesis of β-Mannosides from a Glucose-derived 1,2-Orthoester
Eisuke Kaji* and Yugo Hosokawa
*School of Pharmaceutical Sciences, Kitasato University, Shirokane 5-9-1, Minato-ku, Tokyo 108-8641, Japan
Abstract
A new, stereospecific synthesis of β-mannosides from glucose-derived 1,2-orthoester has been developed using a simple four-step procedure. For the synthesis of β-D-Man-(1→6)-D-Gal, a 6-OH free galactose derivative was glycosylated with the orthoester to yield β-D-Glc-(1→6)-D-Gal; the Glc unit of which was epimerized into the β-mannoside in good yield.
Published online:
■ Regiocontrolled Ring Opening Reactions of a Cyclic Acetal
Yuichiro Egami, Masaru Takayanagi, Keiji Tanino,* and Isao Kuwajima*
*Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
Regiocontrol in ring opening reactions of 2-alkyl-4,4-dimethyl-1,3-dioxolane with allyltrimethylsilane was investigated. In the reactions promoted by TiCl4, the ratio of the isomers can be changed from 91:9 to 1:99 simply by adopting different experimental procedures based on the sequence of adding the substrates.
Published online:
■ A Novel Synthesis of Avermectin B1a from Avermectin B2a
Tadashi Katoh,* Etsuko Itoh, and Shiro Terashima*
*Sagami Central Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
The title synthesis was achieved via a four-step sequence of reactions including selective silylation of the C4”- and the C5-hydroxy groups, mesylation of the remaining C23-hydroxy group, tetra-n-butylammonium oxalate-induced elimination, and deprotection of the silyl protecting groups.
Published online:
■ A Facile Synthetic Method of ABCD Ring System of Antitumor Alkaloid Camptothecin via Intramolecular Hetero Diels-Alder Reaction
Masahiro Toyota,* Chiyo Komori, and Masataka Ihara*
*Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
ABCD ring system of antitumor alkaloid camptothecin (1), basic framework of nothapodytine B (2), was prepared from 2-chloro-3-hydroxy-methylquinoline (4) in 7 steps. The key reaction involves intramolecular hetero Diels-Alder reaction.
Published online:
■ Asymmetric Cyclization of Diene Having an Alkoxy Moiety in a Tether
Yousuke Yamaura and Miwako Mori*
*Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
Asymmetric cyclization of diene having a hydroxymethyl or hydroxyethyl group in a tether gave a trans-product with a high ee derived from trans-zirconacycle, while the ee of a cis-product derived from cis-zirconacycle was low. Coordination of the hydroxy group to zirconium as an intermediary zirconacycle would affect the ee of the cyclized product.
Published online:
■ Chitinase-catalyzed Synthesis of Oligosaccharides by Using a Sugar Oxazoline as Glycosyl Donor
Shin-ichiro Shoda,* Toshitsugu Kiyosada, Hiroyuki Mori, and Shiro Kobayashi*
*Department of Materials Chemistry, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
Abstract
The regio- and stereoselective addition reaction of various methyl glycosides having an N-acetylglucosamine unit to the oxazoline derivative of N-acetyllactosamine has been achieved by using a chitinase as catalyst, giving rise to the corresponding oligosaccharides.
Published online:
■ Diastereoselective Synthesis of α-Butadienyl-β-lactams and Some Stereochemical Aspects of Their Diels-Alder Adducts
Arun K. Sharma, R. Senthil Kumar, and Mohinder P. Mahajan*
*Department of Pharmaceutical Sciences, Guru Nanak Dev University, Amritsar 143005, Punjab, India
Abstract
An efficient diastereoselective synthesis of α-dienyl-β-lactams via [2+2] cycloadditions of imines with butadienyl ketene is reported. The dienyl functionality of α-dienyl-β-lactams was then exploited in Diels-Alder reactions with N-phenylmaleimide (NPM), diethyl fumarate (DEF), ethyl acrylate (EA), 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) and stereochemical aspects of their Diels-Alder adducts are reported.
Published online:
■ Selective Intramolecular Oxyselenenylation of Olefinic Alcohols and Carboxylic Acids by Using Organic Cyanoselenides in the Presence of Metal Triflates
Shizuaki Murata,* Chisato Suzuki, Hirofumi Inoue, Yukihiro Andoh, Yoshihiro Hayasi, and Toshiyasu Suzuki
*Graduate School of Human Informatics, Nagoya University, Nagoya 464-8601, Japan
Abstract
The reagent, ArSeCN—M(OTf)n, is prepared from equimolar amounts of an aromatic selenocyanate and metal trifluoromethanesulfonate. It reacts with unsaturated alcohols and carboxylic acids to give cyclic ethers and lactones, respectively. Depending on conditions, reactions of trans-2-allylcyclohexanol with the reagent selectively afford exo-cyclized tetrahydrofuran or endo-cyclized tetrahydropyran. The mechanism of exo/endo selection is discussed based on molecular dynamics studies.
Published online:
■ Synthesis of 3-Allyl- and 3-Benzyl-Δ3-cephems through Sequential Reductive 1,2-Elimination/Addition/Cyclization of 3,4-Disubstituted 2-Butenoates in Allyl and Benzyl Halides/Mn/NiCl2/AlCl3/NMP Systems
Hideo Tanaka,* Yoshihisa Tokumaru, and Sigeru Torii
*Department of Applied Chemistry, Faculty of Engineering, Okayama University, Okayama 700-8530, Japan
Abstract
One-pot synthesis of 3-allyl- and 3-benzyl-Δ3-cephems through a sequential reductive 1,2-elimination/addition/cyclization of 3,4-disubstituted 2-[2-oxo-3-phenylacetamido-4-(phenylsulfonylthio)azetidin-1-yl]-2-butenoates was successfully performed by treatment with allyl and benzyl halides in an Mn/NiCl2(bpy)/AlCl3/N-methyl-2-pyrroridinone (NMP) system.
Published online:
■ An Expeditious Synthesis of Vibsanol, a Benzofuran-Type Lignan from Viburnum awabuki
Atsushi Sakai, Toyohiko Aoyama,* and Takayuki Shioiri*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Vibsanol (1), a benzofuran-type lignan isolated from the wood of Viburnum aw abuki (Caprifoliaceae), was synthesized from the readily available vanillin; the key step is a tandem cycization of o-tert-butyldimethylsioxydiarylalkyne (2) with tetrabutylammonium fluoride and excess paraformaldehyde.
Published online:
■ A Novel Synthesis of a Highly Sterically Hindered C2-Symmetric Chiral Pyridine Derivative
Hiyoshizo Kotsuki,*Hiromitsu Sakai, Jong-Gab Jun, and Motoo Shiro
*Department of Material Science, Faculty of Science, Kochi University, 2-5-1, Akebono-cho, Kochi 780-8520, Japan
Abstract
A highly sterically hindered C2-symmetric chiral pyridine derivative (3) was synthesized from 1,5-diketone (2) by the action of NH4OAc/Cu(OAc)2 in refluxing propionic acid. The pKa of 3 was determined to be 6.26 and the structure was characterized by X-Ray crystallographic analysis of its triflic acid salt.
Published online:
■ Synthesis and Properties of New Fused Bicyclic Compounds Containing P-B-S Linkages
Eiji Hirakawa, Nobuhiro Takeda, and Tsuneo Imamoto*
*Department of Chemistry, Faculty of Science, Chiba University, Inage, Chiba 263-8522, Japan
Abstract
New bicyclic cimpounds, (P-B)-12-phenyl-12H-dibenzo[d,g][1,3,6,2]dithiaphosphaborocine (3a) and (P-B)-12-cyclohexyl-12H-dibenzo[d,g][1,3,6,2]dithiaphosphaborocine (3b), were synthesized by the reaction of phenyl- and cyclohexylbis(2-mercaptophenyl)phosphine (5a and 5b) with BH3-THF. The structure of 3a and 3b were definitively determined by X-Ray crystallographic analysis. The reaction of tris(2-mercaptophenyl)phosphine (5c) with BH3-THF gave a bicyclic compound, (P-B)-12-{2-[(4-hydroxybutyl)thio]phenyl}-12H-dibenzo[d,g][1,3,6,2]dithiaphosphaborocine (8).
Published online:
■ Synthesis of Dihydropyrroles and Tetrahydropyridines by the Cyclization of O-Methylsulfonyloximes Having an Active Methine Group
Masayuki Yoshida, Katsuya Uchiyama, and Koichi Narasaka*
*Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract
3,4-Dihydro-2H-pyrroles and 2,3,4,5-tetrahydropyridines are prepared by treatment of (E)-O-methylsulfonyloximes having an active methine group at γ- or δ-position with 1,8-diazabicyclo[5.4.0]undec-7-ene via SN2-type substitution on sp2 nitrogen atom of the oxime derivatives.