HETEROCYCLES

■ Biographical Data

Koji Nakanishi*

*Centennial Professor of Chemistry Emeritus, Department of Chemistry, Columbia University, 3000 Broadway, MC 3144, New York, NY 10027, U.S.A.

■ Bibliography

Koji Nakanishi

*Centennial Professor of Chemistry Emeritus, Department of Chemistry, Columbia University, 3000 Broadway, MC 3144, New York, NY 10027, U.S.A.

■ Pre-cerebration of Koji Nakanishi’s 75th Birthday

Mamoru Ohashi

*Department of Chemistry, Faculty of science, Kanagawa University, 2946 Tsuchiya, Hiratsuka 259-1293, Japan

■ Preface

Shosuke Yamamura

*Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku, Yokohama 223-8522, Japan

■ A Tribute to the Contributions of Professor Koji Nakanishi in Heterocyclic Chemistry

Yoko Naya

*The Institute of Food Chemistry, 1-1-1, Wakayamadai, Shimamotocho, Mishimagun, Osaka 618-0024, Japan

■ A Stereoselective Synthesis of 4-O-Methyl- 13-desacetyl-12,13-di-O-benzylcarzinophilin

Masaru Hashimoto and Shiro Terashima*

*Sagami Central Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan

Abstract

The title synthesis was achieved by the synthetic scheme featuring the following four key steps: i) coupling of the methyl thioimidate with the 2-oxazolin-5-one (5+6→13), ii) construction of the C17-C21 functionality by the use of Sharpless asymmetric dihydroxylation and subsequent manipulation of the functional groups (13→→→21), iii) activation of the 4-(pyrrolidin-2-ylidene)-2-oxazolin-5-one system by introducing an Alloc group into N9 position and subsequent ring opening with the L-threonine derivative (21+7→26), and iv) construction of the characteristic 2-methylidene-1-azabicyclo[3.1.0]hexane system with TBAF (30→2).

■ Optical Resolution and Asymmetric Synthesis of Benzyl 3,5-Dimethyl-4-(2,2,2-trifluoro-1-hydroxyethyl)pyrrole-2-carboxylate

Masaaki Omote, Akira Ando, Toshiyuki Takagi, Mayumi Koyama, Itsumaro Kumadaki,* and Motoo Shiro

*Faculty of Pharmaceutical Sciences, Setsunan University, 45-1, Nagaotoge-cho, Hirakata-shi, Osaka 573-0101, Japan

Abstract

For the total synthesis of 3- and 8-(2,2,2-trifluoro-1-hydroxyethyl)deuteroporphyrin dimethyl esters (2, and 3) in a large scale by ring closure, the camphanyl ester (5) of the titled ester (4) was resolved, but hydrolysis of the resolved 5 was unsuccessful. Oxidation of 4 with Dess-Martin reagent gave 3-trifluoromethylcarbonyl compound (6), which was reduced with catecholborane in the presence of a chiral catalyst to a chiral isomer of 4 in a high enantiomeric excess.

■ Absolute Configuration of (+)-PT-Toxin: Enantiodivergent Synthesis of (+)- and (-)-PT-Toxins

Takashi Kamikubo and Kunio Ogasawara*

*Pharnaceutical Institute, Tohoku University, Aramaki, Aoba-ku, sendai 980-77, Japan

Abstract

Absolute configuration of (+)-PT-toxin, isolated from the tea gray blight fungi, Pestalotiopsis longiseta and Pestalotiopsis theae, has been determined unambiguously by enantiocontrolled synthesis of both enantiomers starting from the common chiral-building block.

■ A Synthesis of a C₁-C₇ Building Block for the Enantiomer of Hennoxazole A Utilizing a Regioselective Ring Opening of a Cyclic Acetal

Takayuki Shioiri,* Nigel McFarlane, and Yasumasa Hamada

*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan

Abstract

AC₁-C₇ building block (4) for the enantiomer of hennoxazole A(1), an antivirus and analgesic active marine natural product, was efficiently synthesized from (S)-malic acid utilizing the following key steps: (1) the stereoselective construction of an anti-1,3-diol, (2) the regioselective ring opening of a cyclic acetal, and (3) the oxidative transformation of the olefin into the ketal of the methyl ketone in a one-pot process.

■ Enantioselective Addition of Thiazolyllithium to Aldimines with the Aid of Chiral Ligand. Asymmetric Synthesis of (S)-Doe, a Component of Marine Natural Product, Dolastatin 10

Kiyoshi Tomioka,* Maki Satoh, Daisuke Taniyama, Motomu Kanai, and Akira Iida

*Graduate School of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

The external chiral ligand mediated asymmetric reaction of thiazolyllithium with aldimines was examined. The amino ether (5) gave rise to relatively high selectivity in the reaction of phenylimine, and sparteine (6) provided high selectivity in the reaction of imines bearing an α-methylene group. The reaction was applied to the synthesis of (S)-Doe, a component of antileukemic marine natural product, dolastatin 10.

■ Enantiocontrolled Synthesis of the Functionalized cis-Decalin

Miki Ozaki, Tomoki Omodani, Toshikazu Bando, and Kozo Shishido*

*Institute for Medicinal Resources, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan

Abstract

An enantioselective synthesis of the functionalized cis-decalin (2) has been accomplished employing a highly diastereoselective intramolecular [3+2] dipolar cycloaddition reaction of the optically active nitrile oxide (16) as the key step.

■ Synthesis of Pyrroline via Cyclization of 4-Isocyano-1-siloxy-1-alkene Induced by an Iminium Salt

Masahiro Murakami,* Naoki Hasegawa, Toshio Nagatomi, and Yoshihiko Ito

*Departmene of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

Abstract

4-Isocyano-1-siloxy-1-alkenes, prepared by the fluoride-catalyzed 1,4-addition of α-isocyanocarboxylates to α,β-unsaturated ketones, underwent cyclization on treatment with an iminium salt to afford pyrroline derivatives.

■ Hunterioside B, a Disaccharide Carrying Monoterpenoid Indole Alkaloid, from Hunteria zeylanica

Hiromitsu Takayama,* Sanan Subhadhirasakul, Osamu Ohmori, Mariko Kitajima, Dhavadee Ponglux, and Norio Aimi*

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

Abstract

A new glycosidic indole alkaloid, hunterioside B (3), was isolated from Hunteria zeylanica collected in south Thailand, and the structure was elucidated to be a strictosidinic acid 3’-α-D-glucoside using spectroscopic analysis.

■ Synthetic Study of Neocarzinostatin Chromophore: Stereoselective Synthesis of N-Methylfucosamine and Its α-Glycoside

Toshio Kaneko, Kazunobu Takahashi, and Masahiro Hirama*

*Department of Chemistry, Graduate School of Science, Tohoku University, Aobayama, Sendai 980-8578, Japan

Abstract

Stereoselective glycosylation of cyclopentanol with 2-azido-2,6-dideoxygalactopyranose (2-azidofucose) derivatives and its transformation to N-methylfucosamine was achieved as a model for the synthesis of neocarzinostatin chromophore.

■ Di-functionalization of Alkenes Using an Oxidant Generated from Manganese(II) Chloride under Oxygen: Synthesis ofγ-Lactones

Makoto Hojo, Chikara Murakami, Kaori Ohno, Jun Kuboyama, Shin-ya Nakamura, Hajime Ito, and Akira Hosomi*

*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan

Abstract

Alkenes are oxidatively dichlorinated by stirring with manganese(II) chloride-lithium methoxide under oxygen atmosphere, followed by treatment with conc. hydrochloric acid. This di-functionalization of alkenes can be applied to the chlorolactonization of lithium 4-pentenoates.

■ Synthesis of Diazathia 15- and 18-Crown Ethers and Their Transport Properties for Metal Cations

Kiyoshi Matsumoto,* Masahiro Nogami, Mitsuo Toda, Hideki Katsura, Naoto Hayashi, and Rui Tamura

*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

A new series of the diazathia 15- and 18-crown ethers were prepared by high pressure S_NAr reaction, in which various heteroaromatics were directly connected to their nitrogens. Liquid membrane transport studies demonstrated that the diazathia 18-crown ethers having benzothiazole, benzoxazole, and pyridine rings on their sidearms exhibited Hg²⁺ and Ag⁺ ion selectivity.

■ Diastereoselective Indium-promoted Addition of Functionalized Allyl Bromides to N-Benzyl-2,3-azetidinedione under Aqueous Conditions

Leo A. Paquette* and Methvin B. Isaac

*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.

Abstract

The stereodifferentiation attending the coupling of geometrically stable allylindium reagents to a 2,3-azetidinedione has been assessed and found to operate at a synthetically useful level in most cases.

■ Novel Oxepane Formation by Reductive Cleavage of 1-Methoxymethyl-6,8- dioxabicyclo[3.2.1]octanes

Kenshu Fujiwara,* Akira Amano, Tetsuo Tokiwano, and Akio Murai*

*Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan

Abstract

The introduction of a methoxymethyl group at the C1 position in the 6,8-dioxabicyclo[3.2.1]octane system enabled novel formation of oxepane in reductive cleavage induced by triethylsilane and titanium(IV) chloride.

■ Macrocycles Containing Five Pyrrole Subunits: The Iso-oxopentaphyrin System

Richard G. Khoury, Laurent Jaquinod, Liem T. Nguyen, and Kevin M. Smith*

*Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616, U.S.A.

Abstract

Reaction of a 1,9-difomyl-5-dipyrroketone (11) with a tripyrrane (12) affords a novel pentapyrrolic macrocycle (13) characterized as an iso-oxopentaphyrin (λ_max 787 nm). Along with the iso-oxopentaphyrin, small amounts of oxophlorin (20) and porphyrin (21) are also produced. Mechanistic implications are discussed.

■ A Facile Access to 3-Cephems by Employing Novel Lewis Acid Mediated Reaction

Tomiki Hashiyama,* Hiroaki Arakawa, and Mitsuyoshi Wagatsuma

*Lead Optimization Research Laboratory, Tanabe Seiyaku Co.Ltd., 2-2-50, Kawagishi, Toddda, Saitama 335-8505, Japan

Abstract

A novel and efficient process to afford 3-cephem Δ³ derivatives was established by employing ZnI₂ - NaHCO₃ - DMF system.

■ Synthesis of 1,2-Dihydroisoquinolines by the Reaction of Isoquinoline with Allyltributyltin or Silyl Enol Ethers in the Presence of N-Acylating Agents

Takashi Itoh, Michiko Miyazaki, Kazuhiro Nagata, Hiroshi Hasegawa, Akio Ohsawa,* and Kazuo T. Nakamura

*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan

Abstract

Isoquinolines were allowed to react with allyltributyltin or silyl enol ethers in the presence of N-acylating agents to give 1-substituted 1,2-dihydroisoquinolines in good yields. When a chiral acid chloride was used for an activator, a high diastereoselectivity was observed for the addition. The configuration of a major isomer was elucidated by an X-Ray crystallographic analysis.

■ Stereoselective Hydrogenation of D-Glucose-derived endo-Olefins with a CF₃ Group—Experimental and Theoretical Explanations—

Shuichi Hiraoka, Takashi Yamazaki,* and Tomoya Kitazume

*Department of Bioengineering, Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259 Nagatuta-cho, Midori-ku, Yokohama 226-8501, Japan

Abstract

The unexpected high diastereofacial selectivity in hydrogenation of endo-olefins bearing a CF₃ group by Pd/C under a hydrogen atmosphere was discussed on the basis of experimental results as well as semiempirical molecular orbital calculations.

■ Silica Gel-promoted Synthesis of 1,4-Oxa-thiane Derivatives from β,β'-Dichloro Sulfides

Satoshi Minakata, Masatoshi Mihara, Nozomu Sugoh, and Mitsuo Komatsu*

*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan

Abstract

Treatment of bis(2-chloro-2-phenylethyl) sulfide, prepared from SCI₂ and styrene, with commercially available silica gel in n-hexane and benzene at 30°C for 6 h gave 2,6-diphenyl-1,4-oxathiane in quantitative yield. The cyclization was successfully applied to other β,β’-dichloro sulfides, affording 1,4-oxathiane derivatives.

■ A Synthetic Approach towards the Identification of Periplaneta Sex Pheromones

Hajime Iwamoto, Takeo Harada, Takashi Takahashi,* and Shozo Takahashi

*Chemical Engieering, Faculty of Engineering, Tokyo Instituteof Technology, Meguro-ku, Tokyo 152-8552, Japan

Abstract

Syntheses of the proposed structure of periplanone J (3) and its diastereomer (4), and the discussion on the true structure of PJ based on spectral analysis of 3,4 and the natural PJ are described.

■ A Convenient Synthesis of Fluorine-containing2,5-Epoxynaphth[1,2-b]azepines by Thermally Induced Cyclization of N-Allyl Substituted 2,4-Bis(trifluoroacetyl)-1-naphthylamines

Etsuji Okada,* Takeshi Tomifuji, Hiroshi Tone, Hiroshi Takeuchi, and Masaru Hojo

*Department of Chemical Science andd Engineerring, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan

Abstract

Thermally induced cyclization of N-allyl substituted 2,4-bis(trifluoroacetyl)-1-naphthylamines (4) proceeded easily in refluxing butyronitrile to give the corresponding 7-trifluoroacetyl-5-trifluoromethyl-2,5-epoxynaphth[1,2-b]azepines (5) in excellent yields.

■ Preparation and X-Ray Crystal Structure of a Unique 2:1-Complex of Mercury(II) Chloride and 5-Oxa-2,8-dithiabicyclo[7.4.1]-tetradeca-9,11,13-trien-14-one, a Troponoid Dithio-Crown Ether

Akira Mori,* Kanji Kubo, Nobuo Kato, Hitoshi Takeshita, Masaaki Shiono, and Norio Achiwa

*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

Abstract

5-Oxa-2,8-dithiabicyclo[7.4.1]tetradeca-9,11,13-trien-14-one formed a unique 1:2 complex with HgCl₂, in which each HgCI₂ molecule coordinates to a sulfur atom and the carbonyl group to form a pseudo Cs structure while the free crown ether forms a spiral crystal packing.

■ Asymmetric Synthesis of (R)(-)-Dimethyl Citramalate

Sang-sup Jew,* Hyun-ah Kim, Sam-mi Song, Jung-sook Jang, and Hyeung-geun Park

*College of Pharmacy, Seoul National University, Shillim-Dong, San 56-1, Kwanak-Gu, Seoul 151-742, Korea

Abstract

An asymmetric synthesis of (R)(-)-dimethyl citramalate (1), involving halolactonization by using (S)(-)-proline as a chiral auxiliary, is reported.

■ Total Syntheses of (-)-Polyoxin J and (-)-Polyoxin L

Hiroyuki Akita,* Kimio Uchida, and Keisuke Kato

*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan

Abstract

A convenient synthesis of the N-protected L-carbamoylpolyoxamic acid derivative (7) from 4-O-tert-butyldiphenylsilyl-2,3-isopropylidene-L-threose (8) using vinylmagnesium bromide and its application to the total syntheses of the peptidyl nucleoside antibiotics, polyoxins J (1) and L (2), are described.

■ Synthetic Study of Ustiloxin Analogs: Benzylic Oxidation of 13-Membered Cyclic Peptide by Lead Tetraacetate

Masato Takahashi, Ryuichi Shirai, Yukiko Koiso, and Shigeo Iwasaki*

*Institute of Molecular and Cellular Biosciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan

Abstract

The 13-membered cyclic peptides (5, 6), analogs of phomopsin-ustiloxin class of antibiotics, have been synthesized. Benzylic hydroxyl group was introduced in desired stereochemistry by lead tetraacetate oxidation followed by methanolysis.

■ A Novel Approach to Functionalized Polycyclic Systems; Synthesis of Tetracyclic Compounds by Sequential Rearrangement-Cycloaddition Reactions of 7-Oxa-2,3-dimethylenenorbornene Derivative

Katsuhiro Konno, Hirokazu Tanigawa, and Hiroaki Takayama*

*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1 Suarashi, Sagamiko-machi, Tsukui-gun, Kanagawa 199-0195, Japan

Abstract

The tricyclic diene (6), readily accessible from a novel building block, 4H,6H-thieno[3,4-c]furan 5,5-dioxide (1), reacted with a variety of dienophiles to give the tetracyclic perhydroazulene derivatives (7) in good to high yield.