HETEROCYCLES

■ Rearrangement of (±)-Flavipucine and Its Diastereoisomer. Chemistry of the Transformation Product

Marindar N. Girotra,* Arthur A. Patchett, and Norman L. Wendler

*Division of Merec and Co., Inc, Merck Sharp and Dohme Research Laboratories, Rahway, New Jersey 07065, U.S.A.

Abstract

Flavipucine rearranges under a variety of conditions via bond reorganization involving C-C bond cleavage of the epoxide function to yield the isobutylglyoxal acetal of 3,4-dihydroxy-6-methyl-2-pyridone. Transformations of this product are presented in support of its structure.

■ Rearrangement of a Quinolizidine to Pyrrolo-Azepine by Expansion-Contraction of Cycles. Synthesis of 2-Acyl Indole

André Buzas,* Catherine Retourné, Jean-Pierre Jacquet, and Gilbert Lavielle

*Laboratorie de Synthèse Organique, U. E. R. Sciences, 45100 Orléans-La Source, France

Abstract

Bromination of 1-ethylhexahydroindolo[2,3-a]quinolizidine followed by basic hydrolysis leads to a rearrangement giving a pyrrolo-azepine.

■ <Coupling of (-)-Vindoline with (±)-Eburnamenine, Structure and Stereochemistry of the Dimeric Products

Seiichi Takano,* Susumi Hatakeyama, and Kunio Ogasawara

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

Abstract

Detailed study of the coupling of (-)-vindoline with (±)-eburnamenine is described.

■ Dimsylsodium-induces Rearrangement of Alkylimidates to N-Alkyllactams

Shinzo Kano,* Tsutomu Yokomatsu, Satoshi Hibino, Keiko Imamura, and Shiroshi Shibuya

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

Abstract

Treatment of 1-ethoxy-3,4-dihydro-6,7-dimethoxyisoquinoline (1) with dimsylsodium yielded 2-ethyl-1,2,3,4-tetrahydro-6,7-dimethoxy-1-oxoisoquinoline (2). Similarly, 2-ethoxy-4,5-dihydro-3H-pyrrole (3), 2-ethoxy-3,4,5,6-tetrahydropyridine (5), 7-ethoxy-3,4,5,6-tetrahydro-2H-azepine (7), and 7-ethoxy-3,4,5,6-tetrahydro-4-methyl-2H-azepine (9) were allowed to react with dimsylsodium to give the corresponding N-ethyllactams (4), (6), (8), and (10), respectively, through O to N migration of ethyl group by the catalytic action of dimsylsodium.

■ Asymmetric Synthesis of β-Amino-α,α-dimethylpropionic Acid

Mitsuru Furukawa,* Tadashi Okasara, Hideyoshi Noguchi, and Yukiro Terawaki

*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan

Abstract

Asymmetric synthesis of optically active β-amino-α,α-dimethyl-β-phenylpropionic acid (V) was achieved by the reaction of the chiral Schiff bases with dimethylketene and with the Reformatsky reagent. The specific rotation and the configuration of V were determined by the correlation with authentically prepared R(+)-β-benzoylamino-α,α-dimethyl-6-phenylethanol (X).

■ The N.M.R. and Mass Spectroscopic Studies of 3-Acetyl-5-alkyl-1-benzyl-1,4-dihydropyridines

Eddy Esmans,* Josef Lepoivre, and Frank Alderweireldt

*Labratory of Organic Chemistry, University of Antwerp (RUCA), Groenenborgerlaan 171, B-2020 Antwerp, Belgium

Abstract

A novel series of 3-acetyl-5-alkyl-1-benzyl-1,4-dihydropyridines (alkyl: methyl; ethyl; isopropyl; n-propyl) is synthesised. ¹H-NMR-spectra are discussed. A mass spectral fragmentation is elaborated using high resolution mass measurements, metastable defocusing technique and deuterium labelling.

■ Photochemistry of Bridged Stilbene Oxides

Kazuyoshi Nishiyama, Kiyoyasu Ishikawa, Ila Sarkar, David C. Lankin, and Gary W. Griffin*

*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.

Abstract

The photochemistry of a pair of stilbene oxides in which the 2,3-positions are bridged by three and four methylene groups has been studied and compared with a lower homolog. Evidence is provided that cyclic ylides are produced upon photolysis of these oxiranes in solution at 254 nm. The primary photoproducts derived from the ylides in turn are β-styrylpropio- and β-styrylbutyrophenones, respectively. In the latter case Norrish type I1 cleavage then occurs to give as final products, 1-phenylbutadiene and acetophenone. The bridged oxiranes were shown to be more photostable than their open chain analogs and on the basis of double irradiation experiments it was established that a carbene rather than a conventional diradical process is operative or competes in the ylide photocleavage and ketone formation.

■ Nonclassical Condensed Thiophenes. The Selenolo[3,4-c]thiophene System

Lydia E. Saris and Michael P. Cava*

*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.

Abstract

The first nonclassical selenolothiophenes, namely 1,3-dimethylselenolo[3,4-d]thiophene (1a) and 1,3-dicarbomethoxyselenolo[3,4-c]thiophene (1b), have been generated from appropriate precursors and characterized as trapping products with 1,3-dipolarophiles. These selenolothiophenes are similar to the corresponding thienothiophenes (7a and 7b) in their high reactivity, and consequently less stable than their recently reported selenoloselenophene analogs 7c and 7d.

■ Reaction of Hydrazine with β-Aminocrotononitrile: Synthesis of 2,7-Dimethyl-5-aminopyrazolo[1,5-a]pyrimidine

Alexander McKillop* and Ryszard J. Kobylecki

*School of Chemical Sciences, University of East Anglia, Norwich, Northfolk NR4 7TJ, U.K.

Abstract

Condensation of hydrazine with β-aminocrotononitrile at room temperature gives 6-(3-methyl-5-amino-1-pyrazolyl)crotononitrile, thermal rearrangement of which produces 2,7-dimethyl-5-aminopyrazolo[1,5-a]pyrimidine in excellent yield. Consequently, the various reactions of hydrazine with β-aminocrotononitrile can readily be rationalised.

■ A New Synthesis of Pyrimido[4,5-b]quinoline-2,4(1H,3H)-dione (5-Deazaalloxazine) Derivatives

Keitaro Senga,* Kayoko Shimizu, Sadao Nishigaki, and Fumio Yoneda

*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan

Abstract

Treatment of 6-anilino-1,3-dimethyluracils with dimethylformamide dimethylacetal afforded the corresponding 1,3-dimethylpyrimido[4,5-b]quinoline-2,4(1H,3H)-diones (1,3-dimethyl-5-deazaalloxazines).

■ A New Method for an Epoxidation of Olefins and Its Application to a Biomimetic Type Synthesis of Monoterpenes, Linalyloxides

Tetsuji Kametani,* Hideo Nemoto, and Keiichiro Fukumoto

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

Abstract

Geraniol (1) was transformed into monoterpenes, linalyloxides (4 and 5) along the biogenetic sequence by the oxidation via geranyl o-nitrophenyl selenide (2). This paper also describes a new method for an epoxidation of olefins.

■ Interconversiion between Pyrrolo[1,2-a]indoles and 2,3-Benzazocin-5-ones — A Synthetic Approach to Mitomycins

Tetsuji Kametani,* Kimio Takahashi, Masataka Ihara, and Keiichiro Fukumoto

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

Abstract

Pyrrolo[1,2-a]indoles (3 and 5) were converted to hexahydro-2,3-benzazocin-5-ones (10 and 11) by a novel sequence involving the reduction with sodium borohydride in acetic acid followed by von Braun reaction. The benzazocines 10 and 11 were recyclised to pyrrolo[1,2-a] indoles (4 and 5).

■ Some Recent Work on Protoberberines and Tetrahydroprotoberberines — A Review

Bantwal R. Pai,* Kuppuswamy Nagarajan, Hosbett Suguna, and Sanlaran Natarajan

*Department of Chemistry, Presidency College, Madras 600005, India

Abstract

This review is dedicated to Professor Tetsuji Kametani on his completion of 60 years, the greater part of which he dedicated to enriching our knowledge of the chemistry of alkaloids in general and isoquinoline alkaloids in particular. During the last one decade and more, there has been a continuous stream of publications from his laboratory dealing with various aspects of isoquinoline alkaloid chemistry. We owe a debt of gratitude to him and his colleagues for their rich contributions. mere has been a vigorous school of research in Japan working on isoquinoline alkaloids and therefore, we thought it appropriate to choose the above subject as a token of tribute to Professor Kametani, his cmrkers and all our other Japanese colleagues who have been working in the field of alkaloids. This article has for its background the excellent reviews of Jeffs (P.W. Jefis, "The Alkaloids", ed. by R.H.F. Manske, Academic Press, New York, 1967, V01.9, pp.41-115) and Shamma (M. Shamma, "The Isoquinoline Alkaloids", Academic Press, New York, 1972, pp.268-314). It is by no means exhaustive and only certain aspects of protoberberine chemistry are being highlighted here. The authors may be pardoned if much interesting material has been left out.

■ Isoquinoline Alkaloid Biosynthesis. Speculations on Some Unsolved Problems

S. F. Dyke*

*School of Chemistry, University of Bath, Bath, Avon. BA2 7AY, U.K.

■ Synthetic Approaches to Streptonigrin and Biological Activities on the Quinolinequinone Systems

Satoshi Hibino*

*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

Abstract

The present review covers literatures on synthetic approaches to streptonigrin, metabolite of streptomyces flocculus. A summary of biological activities on the quinolinequinone systems is also presented. The contents of this review are as follows:
1. Introduction
2. Synthetic approaches to the quinoline- quinone systems
3. Synthetic approaches to the pyridine ring systems
4. Biological activities
5. Conclusion

■ New Synthetic Reactions Based on the Onium Salts of Azaaromatic Compounds

Teruaki Mukaiyama*

*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan

■ Photochemistry as a Tool in Heterocyclic Synthesis: Form Pyridinium N-Ylides to Diazepines and Beyond

Jacques Streith*

*Ecole Nationale Supérieure de Chimie de Mulhouse, Université du Haut-Rhin, 68093 Mulhouse, France

■ Reactions of Carbenes with Pyrimidines and Isoquinolines. Synthesis of Modified Nucleosides and Alkaloids

U. K. Pandit*

*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands

■ Photoreactions in the Synthesis of Heterocycles. Designs with Amides and Imides as Synthon Chromophores

Yuichi Kanaoka*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

■ Progress on the Synthesis of Mitosenes

Julius Rebek* and Jean-Claude Gehret

*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.

■ Metal Catalysis in the Synthesis of Heterocycles

K. Barry Sharpless*

*Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, U.S.A.

■ Novel Metalloporphyrins Possessing Biomimetic Function

Zen-ichi Yoshida*

*Faculty of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

■ Heterocyclic Chemistry Related to Porphyrins

Burchard Franck,* Gregor Fels, Günter Ufer, Rolf Steinkamp, Christian Wegner, and Gerhard Bringmann

*Organisch-Chemisches Institut, Universität Münster, Orleansring 23, D-4400 Münster, Germany

■ Improved Synthesis of (+)-Morphine, (+)-Codeine and (+)-Heroin

Kenner C. Rice, Ikuo Iijima, and Arnold Brossi*

*Laboratory of Chemistry, Metabolism and Digestive Diseases, National Institute of Arthritis, Bethesda, Marylanf 20014, U.S.A.

■ Electro-oxidations of Nitrogen Heterocyclic Compounds

James M. Bobbitt*

*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.

■ The Total Synthesis of Dregamine and Epi-dregamine. A General Synthetic Route to 2-Acylindole Alkaloid

James P. Kutney*

*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada

■ Indole Alkaloid Biosynthesis: Partial Purification of "Ajamalicine Synthetase" from Catharanthus roseus Tissue Cultures

A. Ian Scott,* S. L. Lee, and W. Wan

*Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.

■ Bioactive Heterocyclic Compounds

Koji Nakanishi*

*Department of Chemistry, Columbia University, 3000 Broadway, Mail Code 3114, New York, New York 10027, U.S.A.

■ The Thermal Reactions of 2H-Azirines

Hiroshi Taniguchi,* Kazuaki Isomura, and Tatsuyoshi Tanaka

*Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

■ Thermal Rearrangement of Aminomethyl Cyclopropyl Ketones

Hideo Nemoto,* Hideharu Seto, and Tetsuji Kametani

*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan