HETEROCYCLES

■ Curriculum Vitae

Teruaki Mukaiyama*

*Tokyo Chemical Industry Co., Ltd., 6-15-5 (TCI) Toshima, Kita-ku, Tokyo 114-0003, Japan

■ Preface

Ryoji Noyori

*Department of Chemistry, Nagoya University, Chikusa, Nagoya, 464-8602, Japan

■ Contributions of Professor Mukaiyama in Organic Synthesis

Koichi Narasaka

*Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

■ Publication List

Teruaki Mukaiyama*

*Tokyo Chemical Industry Co., Ltd., 6-15-5 (TCI) Toshima, Kita-ku, Tokyo 114-0003, Japan

■ An Expedient Palladium-mediated Route to 3-Arylfurans

Takahiko Taniguchi, Hiroshi Nagata, Regina Mikie Kanada, Kohei Kadota, Miwako Takeuchi, and Kunio Ogasawara*

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan

Abstract

A facile route to 3-arylfurans has been developed by employing the Heck reaction between 2,5-dihydro-2,5-dimethoxyfuran and aryl iodides as the key step.

■ Thermal Ring Transformation of 2,2-Disubstituted Benzothiazoline 1-Oxides

Hiroshi Shimizu,* Michiko Kanematsu, Kiyomi Hashimoto, and Kazuhiro Kobayashi

*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan

Abstract

Thermal rearrangement of 2,2-disubstituted benzothiazoline 1-oxides (1) in aprotic solvent afforded the corresponding 1,4-benzothiazines (2) and (3). The thermal reaction performed in the presence of electron-deficient acetylenic compounds produced new tricyclic compounds (7) whose structures have been established by an X-Ray crystal structure determination.

■ Kinetic Resolution of 5-Hydroxy-2,3,4,5-tetrahydrobenzazepines with Chiral 1,1'-Bi-2-naphthol Derived Acylating Agents

Jun Matsubara, Kenji Otsubo,* Yoshikazu Kawano, Kazuyoshi Kitano, Tadaaki Ohtani, Hiroshi Yamashita, Seiji Morita, and Minoru Uchida

*Tokushima Research Institute, Otsuka Pharmaceutical Co., Ltd., Kagasuno 463-10, Kawauchi-cho, Tokushima, Tokushima 771-0192, Japan

Abstract

(R)-2'-Hydroxy-1,1'-binaphthalene-2-yl benzoate (1a) was found to be an efficient asymmetric acylating agent for a secondary alcohol, 5-hydroxy-2,3,4,5-tetrahydro-1-(p-toluenesulfonyl)-1H-benzazepine (2a), which is a key intermediate for preparing a metabolite of the vasopressin V₂ receptor antagonist, OPC-31260 (4).

■ Palladium-catalyzed Ring Expansion of Hydroxy Methoxyallenylphthalans as a Novel Synthetic Method for Highly Substituted 4-Isochromanone Derivatives

Ill-Yun Jeong, Motoo Shiro, and Yoshimitsu Nagao*

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan

Abstract

The palladium(0)-catalyzed ring expansion reaction using hydroxy methoxyallenylphthalans (3) proceeded smoothly to give highly substituted 4-isochromanone derivatives (4), and treatment of commercially available phthalide (5) with lithium methoxyallene furnished two atom ring-expanded endo-benzoxepin-5-one (8).

■ Fluoride-catalyzed Aldol-Type Reactions of α-Isocyano Esters Producing 2-Oxazoline Derivatives

Yoshihiko Ito,* Noriko Higuchi, and Masahiro Murakami*

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

Abstract

An α-isocyano ester underwent the fluoride-catalyzed aldol-type reaction with an aldehyde to afford a 2-oxazoline derivative.

■ Enantioselective Conjugate Addition of Organometallic Reagents to Cycloalkenones by the Aid of Chiral Lactam-Phosphine Ligand

Kiyoshi Tomioka* and Yuichi Nakagawa

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

Abstract

The chiral lactam-phosphine ligand and copper salt mediated asymmetric conjugate addition reaction of butylmagnesium chloride and diethylzinc with cycloalkenones. Among phosphines examined, 5-((diphenyl-phosphino)methyl)-3,3-dimethylpyrrolidin-2-one (1) gave rise to good selectivity and high yield.

■ Studies Relating to the Synthesis of Laurenenynes: Construction of the Alkylidene Side Chain via [2,3]-Wittig-Still Rearrangement at the Anomeric Center of a Furanoside Derivative

Hideyuki Sugimura,* Yoshiki Hasegawa, and Kenji Osumi

*The Noguchi Institute, 1-8-1, Kaga, Itabashi-ku, Tokyo 173-0003, Japan

Abstract

The construction of the C₆ alkylidene side chain of laurenenynes has been investigated using the [2,3]-Wittig-Stil1 rearrangement at the anomeric position of an appropriate glycofuranoside derivative, followed by further chemical transformations.

■ Multiturn Helical Self-Organization of Extended Alternating Pyridine-Pyrimidine Strands

Masakazu Ohkita, Jean-Marie Lehn,* Gerhard Baum, and Dieter Fenske

*Laboratoire de Chimie Supramoléculaire, ISIC, Université de Louis Pasteur, 4, rue Blaise Pascal, F-67000 Strasbourg, France

Abstract

The preprogrammed achiral oligomers (3) and (4), composed of pyridine-pyrimidine sequences containing up to 27 heterocycles, undergo self-organization into extended multitum helical structures both in solution and in the solid state, with spontaneous chiral resolution of 3 on crystallization.

■ Sulfur-containing Heterocycles: Facile Synthesis of 4H-1,3-Thiazines by the Reaction of 3-N-Acylamino Ketones with Lawesson's Reagent

Mayuko Ori and Takehiko Nishio*

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

Abstract

The treatment of 3-N-acylamino ketones with Lawesson's reagent [LR: 2,4-bis(p-methoxyphenyl)-1,3,2, 4-dithiaphosphetane 2,4-disulfide] afforded the sulfur-containing heterocycles, 4H-1, 3-thiazines in moderate to good yields, along with the corresponding 3-N-thioacylamino ketones.

■ Regioselective Ring-opening Fluorination of Oxetanes with Silicon Tetrafluoride

Makoto Shimizu,* Shigekazu Kanemoto, and Yuko Nakahara

*Department of Chemistry for Materials, Mie University, Tsu, Mie 514-5807, Japan

Abstract

Oxetanes were regioselectively cleaved with silicon tetrafluoride to give γ-fluoro alcohols in good yields, in which effects of additives and stereoselectivities were investigated.

■ Domino-Hydroformylation-Allylboration-Hydroformylation for the Synthesis of trans-2-Alkylpiperidin-3-ols

Reinhard W. Hoffmann,* David Brückner, and Vincent J. Gerusz

*Fachbereich Chemie, Philipps-Universität Marburg, D-35032 Marburg, Germany

Abstract

Hydroformylation of an N-allyl-γ-amidoallylboronate (7d) generates a formyl function which allows intramolecular allylboration to proceed to give a vinylpiperidinol (11). The latter is again hydroformylated under the reaction conditions to furnish an oxa-aza-decalin ring system (12).

■ Substituent Effects on the Control of Cationic Isomerization and Polymerization of Five-membered Cyclic Dithiocarbonates

Wonmun Choi, Fumio Sanda, and Takeshi Endo*

*Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan

Abstract

The electrophilic reactions of five-membered cyclic dithiocarbonates were studied. They afforded the isomers and polymers depending on the substituents.

■ A Practical Synthetic Method for α- and β-Glycosyloxyacetic Acids

Tadakatsu Mandai,* Hiroshi Okumoto, Tetsuta Oshitari, Katsuyoshi Nakanishi, Katsuhiko Mikuni, Ko-ji Hara, and Ko-zo Hara

*Department of Chemical Technology, Kurashiki University of Science & the Arts, 2640 Nishinoura, Tsurajima-cho, Kurashiki 712-8505, Japan

Abstract

Dihydroxylation of allyl 2,3,4-tri-O-benzyl-6-O-tritylglycosides provides diols, the anomers of which can easily be separated by column chromatography in a practical scale. These anomers can be cleanly transformed into α- and β-glycosyloxyacetic acids, respectively, via oxidative cleavage of the diol followed by oxidation.

■ Novel Intramolecular Radical Ar-C Glycosylation-Lactonization Reaction in the Transformation of Capuramycin

Hitoshi Hotoda,* Makiko Daigo, Toshio Takatsu, Akiko Muramatsu, and Masakatsu Kaneko

*Exploratory Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan

Abstract

Radical deoxygenation of capuramycin derivative (2a,b) gave the unexpected lactone (3a,b) in moderate yield via a novel intramolecular radical Ar-C glycosylation-lactonization reaction. R-115381 and R-116022, thus obtained, showed weak antimicrobial activity against several Gram-positive bacteria.

■ Stereospecific Synthesis of Piperidine Skeleton by [4+2] Cycloaddition, Leading to the Synthesis of Piperidines of Biological Interests

Makoto Shimizu,* Akihiko Arai, and Tamotsu Fujisawa

*Department of Chemistry for Materials, Mie University, Tsu, Mie 514-5807, Japan

Abstract

[4+2] Cycloaddition reaction between a chiral imine possessing an auxiliary derived from tartaric acid and Danishefsky diene was studied, and the reaction promoted by boron trifluoride etherate gave 2,3-dehydropiperidin-4-one in a stereospecific manner. The adduct thus obtained was converted into (S)-coniine derivatives without loss of the stereochemical integrity.

■ Syntheis of Zeaxanthin- and Cryptoxanthin-β-D-glucopyranosides

Yumiko Yamano, Yoshitsugu Sakai, Satomi Yamashita, and Masayoshi Ito*

*Kobe Pharmaceutical University, Motoyamakita-machi, Higashinada-ku, Kobe 658-8558, Japan

Abstract

β-Glucosidation of (3R)-3-hydroxy-β-ionone (6) was achieved in a reasonable yield by use of tetra-O-benzoyl-α-D-glucopyranosyl bromide (8c) as a glycosyl donor and silver triflate as an activator. The resulting glucoside (9) was transformed into the β-apo-12’-carotenal (18), which was condensed with the Wittig salt (19) or (20) to provide zeaxanthin-mono-β-D-glucopyranoside (3) or cryptoxanthin-β-D-glucopyranoside (4).

■ Preparation of Cyclic Amines by the Titanocene(II)-promoted Cyclization of Thioacetals Having a Carbon-Carbon Double Bond

Tooru Fujiwara, Yoshiko Kato, and Takeshi Takeda*

*Department of Applied Chemisry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan

Abstract

Nitrogen-containing unsaturated heterocycles were obtained in good yields by the titanocene(II)-promoted ring-closing metathesis of the amines possessing an olefin and a diphenyl thioacetal moieties.

■ Synthesis of Chiral α-Acetoxy-N-acetylamides from Chiral Pyrimidylalkanols by the Oxidative Cleavage of Pyrimidine Ring

Shigehisa Tanji, Yasutaka Kodaka, Takanori Shibata, and Kenso Soai*

*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan

Abstract

Acetates of chiral 5-pyrimidylalkanols are transformed into chiral α-acetoxy-N-acetylamides and α-acetoxyamides without racemization in high total yields by the oxidative cleavage of pyrimidine ring using ruthenium tetroxide.

■ Syntheses, Spectroscopic Properties, and Polymerizations of 2,2'-Bitellurophene, 2,2':5',2"-Tertellurophene, and Related Hybrid Terchalcogenophenes

Shinobu Inoue, Tetsuya Jigami, Hiroshi Nozoe, Yoshio Aso, Fumio Ogura, and Tetsuo Otsubo*

*Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8527, Japan

Abstract

2,2'-Bitellurophene, 2,2':5',2"-tertellurophene, and related hybrid terchalcogenophenes have been synthesized as a novel extended series of tellurophene homologues. The molecular and crystal structures of 2,2'-bitellurophene were elucidated by an X-ray crystallographic analysis and compared with those of 2,2'-bithiophene and 2,2'-biselenophene. The molecular structure adopts an almost completely planar transoid conformation, as seen for the other bichalcogenophenes, but the crystal structure is quite different, comprising a unique herringbone-type of molecular packing with heteroatomic interactions of tellurium. The electronic absorption spectra of the tellurophenes are characterized by strong π-π* transitions which appear in the longer wavelength region than those of thiophene and selenophene analogues and are systematically red-shifted with the increasing number of the conjugated tellurophene units. On the other hand, the emission spectra suffer marked extinction owing to a heavy atom effect of tellurium, and only the extended tertellurophene shows weak fluorescence in the visible region. The elevation of the HOMO levels of the tellurophenes is suggested by low oxidation potentials in the cyclic voltammograms. Consequently, ready electrolytic and chemical oxidative coupling reactions occur to give filmy or powdered polytellurophenes, whose conductivities are wide-ranging with the order of 10^-3-10^-9 Scm^-1, depending on the original tellurophene species and the polymerization conditions.

■ Oxetane Formation by 1,3-Migration of Benzyloxy Group in 7-Oxabicyclo[2.2.1]hept-2-yl Cations: Synthesis of 4,7-Dioxatricyclo[3.2.1.0^3,6]octane and 2-Oxabicyclo[2.2.2]octane Encrusted in the 1,4:5,8-Diepoxy-perhydrophenanthrene Ring System

Hervé Mosimann and Pierre Vogel*

*Section de Chimie de l’Université, BCH, CH-1015-Lausanne-Dorigny, Switzerland

Abstract

Epoxidation of (1RS,2SR,3SR,4RS,6RS,7RS,8RS,12RS,13RS)-6,13-bis(benzyloxy)-15, 16-dioxapentacyclo[10.2.1.1^4.7.0^2,11.0^3.8]hexadec-10-en-8-yl-methanol (12) led to the stereoselective formation of (1RS,2RS,3RS,5RS,6SR,7RS,8RS,10RS,11SR,12SR,16SR)-3,10-bis(benzyloxy)-13,17,18-trioxahexacyclo[10.2.2.1^2,5.1^8,11.0^1.6.0^7.12]octadecan-16-ol (13). Epoxidation of the acetate (19) derived from 12 gave an epoxide (20) that generated (1RS,2SR,3RS,4RS,6RS,7SR,8RS,9SR,11RS,12RS,13RS)-13-benzyloxy-9-hydroxy-15,16,17-trioxahexacyclo[10.2.1.1^4,7.1^6,8.0^2,11.0^3,8]heptadecane-11-methyl acetate (21) under acidic conditions. These reactions imply the formation of 2-alkyl-6-endo-benzyloxy-7-oxabicyclo[2.2.1]hept-2-yl cation intermediates (e.g. 14) that are quenched intramolecularly by the hydroxymethyl group to give the corresponding 2-oxabicyclo[2.2.2]octane systems (12→13). In the case of the acetoxymethyl containing intermediate, the latter cyclization is retarted and a facile 1,3-migration of the endo-benzyloxy group occurs leading to the corresponding 4,7-dioxatri-cyclo[3.2.1.0^3,6]octane derivative (20→21).

■ A New Simple Procedure for the Isomerization of 2-Furylcarbinols to Cyclopentenones

Maurizio D'Auria

*Dipartimento di Chimica, Università della Basilicata, Via N. Sauro 85, 85100 Potenza, Italy

Abstract

The previously reported acid catalyzed isomerization of 2-furylcarbinols to 5-alkyl-4-hydroxycyclopent-2-enones was performed in boiling water in the absence of any acid catalyst. In this case the reaction led to the formation of more stable isomer 2-alkyl- or 2-aryl-4-hydroxycyclopent-2-enones. The reaction of chiral 2-furylcarbinol in the presence of zinc chloride gave a racemic cyclopentenone while 2-furylcarbinol did not undergo racemization. A new mechanism for the conversion of 2-furylcarbinols into cyclopentenone is proposed.

■ Novel Palladium Chiral Phosphinooxazoline Complexes: Crystal Strucutre Studies and Application to Asymmetric Heck Reaction

Masamichi Ogasawara, Kazuhiro Yoshida, and Tamio Hayashi*

*Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan

Abstract

The novel palladium(II) complexes coordinated with (S,S)- and (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-diphenylphosphino-1,1'-binaphthyls (1a and 1b) were prepared and their structures were determined by X-Ray crystallography. The X-Ray single crystal structure studies reveal that the axially chiral binaphthyl skeletons are more strongly regulating the chiral environment around the palladium centers than the chiral carbon centers in the oxazoline moieties. The results from application of 1a and 1b to the asymmetric Heck reaction also supported this conclusion. The highest enantioselectivity (88% ee) was observed in (R)-2-phenyl-2,5-dihydrofuran which was obtained from 2,3-dihydrofuran and phenyl triflate catalyzed by Pd/1a.

■ Novel Heterocyclic Analogs of Trityl Radicals: Synthesis and Dimerization of Diarylmethyl-1H-1,2,4-triazoles and Diarylmethyl-2H-phenanthro[9,10-d]-1,2,3-triazoles

Alan R. Katritzky,* Baozhen Yang, David P. M. Pleynet, and Jin Wang

*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville FL 32611-7200, U.S.A.

Abstract

Diarylmethanes 1a-h, 9a-i and 12 containing a heterocyclic group attached to the central carbon atom have been synthesized. Lithiation of these substrates followed by the addition of iodine gave dimers 2a,b,d,e and 10 via α, para-dimerization of novel heterocyclic diarylmethyl radical intermediates.

■ Preparation of New Nitrogen-bridged Heterocycles. 47. Reactions of 2-Indolizinethiolates with Acetylenic Compounds

Akikazu Kakehi,* Suketaka Ito, Hiroyuki Suga, Hiroyuki Takahashi, and Kazuhiro Dobashi

*Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan

Abstract

The reactions of potassium 2-indolizinethiolates having an ester group at the 3-position with some electron deficient acetylenic compounds were investigated. Their Michael additions or Michael addition-cyclizations proceeded with the elimination of an ester group to provide the corresponding 2-vinylthioindolizine and 4H-thiino[2,3-b]indolizin-4-one derivatives.

■ Highly Diastereoselective Reduction of γ-Keto Amides: Diastereoselective Synthesis of γ-Butyrolactones with Contiguous Chiral Centers

Masami Satoh, Sakurako Washida, Sawako Takeuchi, and Morio Asaoka*

*Department of Chemical and Biological Sciences, Faculty of Science, Japan Women's University, 2-8-1 Mejirodai, Bunkyoku, Tokyo 112-0015, Japan

Abstract

Diastereoselective reduction of γ-keto amides, which were easily prepared by the reaction of a zinc homoenolate of butanamide with acid chlorides in the presence of Pd(0) catalyst, was achieved. Cyclization of the products, γ-hydroxy amides, under various conditions gave α,β-disubstituted and α,β,γ-trisubstituted γ-butyrolatones with high diastereoisomeric purities.

■ Pseudoesters and Derivatives. Part 38. 1,3-Dipolar Cycloadditions of Aryl Azides and an Aziridine, via Azomethine Ylide, to 2(5H)-Furanones Substituted at the 5-Position by Methoxy and Sulfur Bearing Group

Gemma Gonzalez, M. Victoria Martín, and M. Carmen Paredes*

*Instituto de Química Orgánica General, C. S. I. C., Juan de la Cierva 3, 28006 Madrid, Spain

Abstract

The behavior of the 2(5H)-furanones (1-3) towards p-methoxy- and p-nitrophenyl azides (4 and 12) has been investigated, in particular with respect to the regio- and stereoselectivity. The 1,3-dipolar cycloaddition of the azometbine ylide generated by thermal ring opening of dimethyl trans-1-(p-methoxyphenyl)aziridine-2,3-dicarboxylate (22) to 2(5H)-furanones (1-3) proceeds in good yield and affords functionalized furo[3,4-c]pyrrol-3-one derivatives.