Special Issue

Robert B. Woodward's Special Issues, Vol. 7, No. 1, 1977

63 data found. 31 - 60 listedFirst Previous Next Last
Communication | Special issue | Vol 7, No. 1, 1977, pp. 227 - 230
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DOI: 10.3987/S-1977-01-0227
Sodium 4,6-Diphenyl-1-oxido-2-pyridone: Reagent for the Conversion of Primary Halides into Aldehydes

Michael J. Cook,* Alan R. Katritzky,* and George H. Millet

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


The title compound readily reacts with primary halides to yield stable 1-alkoxypyridones VI which are smoothly converted thermally to aldehydes and non-volatile 4,6-diphenylpyridone. The intermediate 1-alkoxypyridones VI form convenient crystalline derivatives for alkyl and benzyl halides.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 231 - 235
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DOI: 10.3987/S-1977-01-0231
An Improved Synthesis of 2,6-Diphenyl-4H-thiopyran-4-one

Chin H. Chen*

*Research Laboratories, Eastman Kodak Company, Rochester, New York 14650, U.S.A.


2,6-Diphenyl-4H-thiopyran-4-one (3) was prepared in high yield by a Pummerer rearrangement of 2,6-diphenyl-4H-dihydrothiopyran-4-one-1-oxide (2) in the presence of trifluoroacetic anhydride. Acid-catalyzed thermal rearrangement of 2 afforded the isomeric 2-benzylidene-3-keto-5-phenyl-1,2-dihydrothiophene (4).

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 237 - 240
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DOI: 10.3987/S-1977-01-0237

Franciscus Freijee, Gerrit Schat, Raymond Mierop, Cormelis Blonberg, and Friedrich Bickelhaupt*

*Department of Organic and Inorganic Chemistry, Faculty of Chemistry, Vrije Universiteit Amsterdam, De Boelelaan, 1083 NL-1081 HV Amsterdam, The Netherlands


In a novel ring cleavage reaction “Rieke-magnesium” and tetrahydrofuran at 100 °C yielded 1-oxa-2-magnesia cyclohexane (I) in up to 50% yield.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 241 - 246
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DOI: 10.3987/S-1977-01-0241
The Ring Cleavage of 3,5-Disubstitutted Isoxazolium Salts with Alkoxides

Choji Kashima,* Nobuhiro Mukai, Yasuhiro Yamamoto, Yoshihiko Tsuda, and Yoshimori Omote

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


This paper communicates the reaction of 3,5-disubstituted N-alkylisoxazolium salts with alkali alkoxide in alcohol to give the β-aminoenones. Also, this reaction was applied to the synthesis of curcumin.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 247 - 250
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DOI: 10.3987/S-1977-01-0247
Ketenimine Carboxylate Isomer Protonation

Darrell J. Woodman,* William H. Campbell, and Eugene F. DeRose

*Department of Chemistry, University of Washington, Seattle, WA 98195-1700, U.S.A.


A reactive C-monosubstituted malonimide has been isolated from ring opening of a 3-unsubstituted isoxazolone followed by isomerization of the intermediate ketenimine carboxylate in HMPA, protonation, and rapid work-up.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 251 - 257
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DOI: 10.3987/S-1977-01-0251
Localisation of Substituents in Porphyrins: The Mass Spectrometric Fragmentation Behavior or Meso-substituted Porphyrinogens

Herbert Budzikiewicz* and Wilma Neuenhaus

*Institut für Organische Chemie, Universität zu Köln, Greinstraße 4, D-50939 Köln 41, Germany


The mass spectra of meso-substituted porphyrinogens are analysed with respect to a possible localisation of substituents in the porphyrin ring system.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 259 - 263
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DOI: 10.3987/S-1977-01-0259
The Reaction of 3,5-Dimethyl-1,4-dinitropyrazole with Amines. A Novel Reaction of a N-Nitropyrazoles

Clarisse L. Habraken* and Steven M. Bonser

*Division of Pharmacognosy, Gorlaeus Laboratories, Leiden University, P.O.Box 9502, Einsteinweg 55, 2300 RA Leiden, The Netherlands


The reaction in alcohol solution of 3,5-dimethyl-1,4-dinitropyrazole (4) with the secondary amines (5a-b) and with triethylamine (10) afford 3(5)-hydroxymethyl-5(3)-methyl-4-nitropyrazole (7) and the 3(5)-alkoxymethyl-5(3)-rnethyl-4-nitropyrazoles (8a-c) presumably formed via an elimination-addition mechanism involving a diazafulvene intermediate (9).

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 265 - 272
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DOI: 10.3987/S-1977-01-0265
Mimosine, Mimosinamine and 3,4-Dihydroxypyridine

Noel K. Hart, Albert Hofman, John A. Lamberton,* and Colin M. Richards

*Division of Applied Organic Chemistry, CISRO, P. O. Box 4331, Melbourne 3001, Australia


A new extraction method has made mimosine easily available. (±)-Alanine formed in the acid hydrolysis of mimosine appears to be a secondary product derived from pyruvic acid by a transamination reaction. Alkylation and acylation reactions of 3,4-dihydroxypyridine are described and mimosinamine has been prepared in low yield.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 273 - 276
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DOI: 10.3987/S-1977-01-0273
Remote Photocyclization. Photochemical Macrocyclic Synthesis with N-(ω-Methylanilino)alkylphthalimides

Minoru Machida, Haruko Takeuchi, and Yuichi Kanaoka*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan


Upon irradiation a homologous series of N-(ω-methylani1ino)alkylphthalimides 4 undergo regioselective remote photocyclization to give medium- to large-sized diazacyclols 5.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 277 - 286
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DOI: 10.3987/S-1977-01-0277
Direct and Sequential Removal of Phenolic Oxygen Functions in S-(+)-Bulbocapnine, S-(+)-Boldine and R-(-)-Apomorphine

Arnold Brossi,* Mohamad F. Rahman, Kenner C. Rice, Max Gerecke, Rene Borer, Jay P. O’Brien, and Sidney Teitel

*Medical Chemistry Section, Laboratory of Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.


Three poly-oxygenated aporphines have been transformed into a variety of desoxy congeners. This was readily accomplished by O-dealkylation with BBr3 and BCl3 to cleave methoxyl and methylenedioxy groups, respectively, followed by reductive elimination of the resulting phenols as their tetrazoyl ethers or diethyl phosphate esters. The simultaneous elimination of two o-positioned hydroxy groups by these procedures was difficult to accomplish without racemization.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 287 - 291
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DOI: 10.3987/S-1977-01-0287
One Step Synthesis of Optically Active Aziridine with Optically Active o-Methoxyphenyl Phenyl Sulfilimine and Olefin

Toshiaki Yoshimura, Takeshi Akasaka, Naomichi Furukawa, and Shigeru Oae*

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


Optically active 2-acylaziridines were synthesized in one step by treating optically active o-methoxyphenyl phenyl sulfilimine with α,β-unsaturated ketones in various solvents.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 293 - 299
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DOI: 10.3987/S-1977-01-0293
Nitrone Ionization Potentials and Cycloaddition Regioselectivities

K. N. Houk,* Alex Bimanand, Debabrata Mukherjee, Joyner Sims, Yau-Min Chang, D. C. Kaufman, and Linda N. Domelsmith

*Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803-1804, U.S.A.


In agreement with theoretical predictions, the “normal” preference for formation of 5-substituted isoxazolines in 1,3-dipolar cycloadditions of nitrones to substituted alkenes changes to a preference for the 4-substituted adduct as the ionization potential of the nitrone decreases, or that of the alkene increases.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 301 - 306
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DOI: 10.3987/S-1977-01-0301
Synthesis and Reaction of Optically Active 2-Aryl-cis- and trans-hexahydro-3,1,4-benzoxazones

Hiroyuki Nohira,* Kyoko Watanabe, Tomohisa Ishikawa, and Kazuhiko Saigo

*Department of Applied chemistry, Faculty of Engineering, Saitama University, Saitama, Saitama 338-8570, Japan


The titled compounds (II) were prepared from the corresponding optically active N-aroyl-cis- and trans-2-aminocyclohexanecarboxylic acids (I) by the action of thionyl chloride and successive treatment with triethylamine. The oxazones readily reacted with alcohols and amines to give the corresponding esters (VI) and amides (VII), providing a convenient method for the resolution of racemic alcohols.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 307 - 314
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DOI: 10.3987/S-1977-01-0307
Stereospecific Cyclization of p-Quinol Acetates to Homoproaporhines

Hiroshi Hara, Osamu Hoshino, Bunsuke Umezawa,* and Yoichi Iitaka

*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan


A sole homoproaporphine (Dienone II) not contaminated with another diastereoisomer (kreysiginone) was obtained as a by-product on acid treatment of a p-quinol acetate (4). Absolute configuration of Dienone II was determined by X-ray crystallographic analysis and mechanism of the stereospecific formation of Dienone II was suggested.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 315 - 320
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DOI: 10.3987/S-1977-01-0315
Synthesis of Adamantane Derivatives. 39. Synthesis and Acidolysis of 2-Azidoadamantanes. A Facile Route to 4-Azahomoadamant-4-enes

Tadashi Sasaki,* Shoji Eguchi, and Nao Toi

*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan


2-Azidoadamantanes 10b-f; and 4-azahomoadamant-4- enes 11a-e were obtained in good yields on treatment of the corresponding alcohols 9a-5 with NaN3 in 57%- H2SO4-CH2Cl2 and in CH3SO3H-CHCl3, respectively. Azides 10a-e gave also 11a-e on decompositions in CH3SO3H-CHCl3, while 10f afforded only adamantylideneaniline.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 321 - 326
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DOI: 10.3987/S-1977-01-0321
Enamine-singlet Oxygen Reactions. Synthesis of β-Lactams from Esters of Azatidine Carboxylic Acids

Harry H. Wasserman,* Bruce H. Lipshutz, and James S. Wu

*Department of Chemistry, Yale University, P.O. Box 6666, New Haven, Connecticut 06511, U.S.A.


Azetidine carboxylic esters may be converted to enol silyl ethers which, as enamino ketene acetals, undergo ready oxidative cleavage of the carbon-carbon double bond by dye-sensitized photooxygenation to form β-lactams.

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Communication | Special issue | Vol 7, No. 1, 1977, pp. 327 - 339
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DOI: 10.3987/S-1977-01-0327
Application of Carbon-13 NMR Spectroscopy to the Structural Elucidation of C19-Diterpenoid Alkaloids from Aconitum and Delphinium Species

S. William Pelletier,* Naresh V. Mody, Rajinder S. Sawhney, and J. Bhattacharyya

*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.


The carbon-13 nuclear magnetic resonance spectra of the aconitine-type diterpenoid alkaloids pseudaconitine, indaconitine, veratroyl-pseudaconine, falaconitine, mithaconitine as well as the lycoctonine-type diterpenoid alkaloids browniine, 14-acetylbrowniine, delphatine, delcosine, 14-acetyldelcosine, delsoline, lycoctonine, tricornine, anthranoyllycoctonine, ajacine, methyllycaconitine and “delsemine” have been determined at 25.03 and 15.03 MHz in the Fourier mode. The signal due to each carbon atom in these alkaloids has been assigned with the help of proton decoupling techniques, additivity relationships and the effects induced by certain structural changes. Previously published carbon-13 chemical shift assignments for the alkaloids browniine and lycoctonine are corrected. Carbon-13 nmr data have also been applied in the structural determination of several previously unknown alkaloids isolated from Aconitum falconeri, Delphinium ajacis and Delphinium tricorne.

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Report | Special issue | Vol 7, No. 1, 1977, pp. 341 - 346
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DOI: 10.3987/S-1977-01-0341
Isolation and Structure Elucidation of Gancidin W

Tikam C. Jain,* John J. Dingerdissen, and Jerry A. Weisbach

*Chemical Reserch and Development, Smith Kline and French Laboratories, Philadelphia, PA 19101, U.S.A.


The antibiotic gancidin W has been shown to be a cyclodipeptide containing leucine and proline moieties.

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Report | Special issue | Vol 7, No. 1, 1977, pp. 347 - 352
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DOI: 10.3987/S-1977-01-0347
Studies on Potential Antitumor Agents (II). Thiosemicarbazones of p-Bromophenyl- and o-Chlorophenylpyridine-2-carboxaldehydes

Lian-Fang Lin, Shwu-Jiuan Lee, and Chao-Tung Chen*

*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.


Thiosemicarbazones of eight p-bromophenyl- and o-chlorophenylpyridine-2-carboxaldehydes have been synthesized. Tumor-inhibitory potency and host toxicity of these compounds were assessed in mice bearing Sarcoma 180 ascites cells.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 353 - 390
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DOI: 10.3987/S-1977-01-0353
1-Azirine Ring Chemistry

Vasu Nair* and Ki Hyup Kim

*Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, U.S.A.


The chemistry of the highly-strained small-ring heterocycle, 1-azirine, has been vigorously pursued in the last decade. This article attempts to highlight the major contributions in this area from the viewpoint of both synthetic and mechanistic organic chemistry.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 391 - 427
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DOI: 10.3987/S-1977-01-0391
Studies in the Heterocyclic Seroes. XII. The Chemistry and Applications of Aza- and Thia-analogs of Phenoxazine and Related Compounds

Charles O. Okafor*

*Department of Chemistry, University of Nigeria, Nsukka, Nigeria


Interest in naturally occurring and synthetic phenoxazine derivatives prompted the synthesis of new rings derived from phenoxazine. Replacement of the benzene rings with pyridine, pyrazine, furan and pyrrole or a combination of them led to novel pyrrolobenzo[1,4]oxazine, furanobenzo[1,4]oxazine, 1,4-diaza- and 1,9-diazaphenoxazines. This article provides a survey of the chemistry and applications of novel heterocyclic ring analogs of phenoxazine and the related dibenzoxazepines and -oxazocines.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 429 - 452
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DOI: 10.3987/S-1977-01-0429
Synthesis and Some Physical and Photochemical Properties of Dinucleortide Analogs

Krzysztof Golankiewicz*

*Department of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland


The dinucleotide analogs in which purine or pyrimidine bases are linked together by the polymethylene chains appeared to be excellent models for the studies of unbonded base-base interactions and photodimerization in nucleic acids. This article gives a survey of recent results obtained in this field in our Laboratory.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 453 - 485
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DOI: 10.3987/S-1977-01-0453
9-Borabicyclo[3.3.1]nonane. A Most Unusual Heterocyclic Dialkylborane

Herbert C. Brown* and Clinton F. Lane

*Richard B. Wetherill Laboratory, Purdue University, West Lafayette, Indiana 47907-1393, U.S.A.


The cyclic hydroboration of 1,5-cyclooctadiene provides 9-borabicyclo[3.3.1]nonane, an unusual boraheterocycle, with interesting chemical properties and unusual characteristics as a hydroborating and reducing agent.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 487 - 506
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DOI: 10.3987/S-1977-01-0487
A Remarkable Rearrangement of Lithium Dialkyl-9-borabicyclo[3.3.1]nonane “Ate” Complexes

Gary W. Kramer and Herbert C. Brown*

*Richard B. Wetherill Laboratory, Purdue University, West Lafayette, Indiana 47907-1393, U.S.A.


Lithium dialkyl-9-borabicyclo[3.3.1]nonane “ate” complexes react via hydride transfer with a variety of reducible organic substrates providing a simple synthesis of the cis-bicyclo[3.3.0]oct-1-yldialkylboranes and their derivatives.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 507 - 527
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DOI: 10.3987/S-1977-01-0507
Recent Developments in the Synthesis of Heterocycles from Enamines and Isothiocyanates

Srinivasachari Rajappa*

*CIBA-GEIGY Research Centre, Goregaon Bombay 400063, India


A serendipitous synthesis of multifunctional thiophene derivatives is described. Nitroenamine-isothiocyanate adducts have been used to prepare 3-nitrothiophenes, 4-nitroisothiazoles, 5-nitropyrimidines and 4-nitropyrazoles.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 529 - 545
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DOI: 10.3987/S-1977-01-0529
Fascinating Problems in Organic Reaction Mechanism VIII: Reactions and Rearrangements of Phenanthraquinone Monoimine

S. Ranganathan* and C. S. Panda

*Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India


Phenanthraquinone monoimine, being the only stable 1,2-diketone monoimine has contributed significantly towards the transformation of diketone monoimines to diverse types of heterocyclic systems. Additionally, the structural work relating to “Phenanthraquinoneimide Anhydride” discovered in 1879 has led to discernment of some interesting transformations associated with heterocyclic systems. This article provides an integrated account of the development in this area and incorporates our own unpublished work.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 547 - 591
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DOI: 10.3987/S-1977-01-0547
Synthesis of Steroidal Heterocycles

A. V. Kamernitzky* and A. M. Turuta

*Institute of Organic Chemistry, Russia Academy of Science, 117913, Moscow, Russia


Heterocyclic steroids have attracted a great deal of attention. This is for two reasons. In the first place, the quantity of the compounds isolated from natural sources is increasing. Secondly, biological properties of heterocyclic steroids have proved to be of interest. That is rather large sphere of investigations that includes the total synthesis which has been reviewed elsewhere1; for the reasons will not be discussed here. The review presented below is intended to cover steroids with additional heterocyclic ring built on to the steroid nucleus in different positions of the molecule. Furthermore, the authors will restrict themselves to discussing of steroids in which five- or six-membered heterocycle with two hetero-atoms in 1’,3’-position is attached to the intact cyclopentaphenanthrene skeleton. During in the past 10 years this field has been extensively investigated and practically has not been reviewed.2-4

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Review | Special issue | Vol 7, No. 1, 1977, pp. 593 - 614
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DOI: 10.3987/S-1977-01-0593
Dihydropyridines in Biosynthesis and Synthesis

James P. Kutney*

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


A summary of experiments relating to the role of dihydropyridines as possible intermediates in the biosynthesis of indole alkaloids and performed in the author’s laboratory is presented. In relation to these interests a series of investigations concerning the stabilization of dihydropyridine systems by means of chromium carbonyl complex formation is described. Some examples of the utilization of such intermediates in synthetic areas are also presented.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 615 - 635
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DOI: 10.3987/S-1977-01-0615
Syntheses of Quinazolone Alkaloids and Benzoxazinones by Retro Mass Spectral Synthesis and Related Analysis

Tetsuji Kametani* and Keiichiro Fukumoto

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


Total synthesis of quinazolone and indoloquinazolone alkaloids by an analysis based on retro mass spcetral synthesis is described. Moreover this account mentions a simple synthesis of quinazolone alkaloids and benzoxazinones by a synthetic procedure developed from retro mass spectral synthesis.

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Review | Special issue | Vol 7, No. 1, 1977, pp. 637 - 659
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DOI: 10.3987/S-1977-01-0637
Nitrite and the Environment. The Nitrosation of α-Amino Acid Derivatives

Raymond Bonnett* and Popi Nicolaidou

*Department of Chemistry, Queen Mary College, Mile End Road, London E1 4NS, U.K.


The reaction of nitrous acid with α-amino acid derivatives is reviewed in the context of the environmental hazard of N-nitrosamines. The reaction products from derivatives of proline, tryptophan, tyrosine, methionine, cysteine, arginine and lysine are discussed.

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