Non-tryptamines

Non tryptamines.—Details of the structure elucidation of seven pyranocarbazole alkaloids of Murraya koenigii [mahanimbine, koenimbine, (-)-mahanine, koenine, koenigine, koenidine, and ( + )-isomahanimbine] have now been published.Mur-rayacine, a minor alkaloid of the same plant, has been isolated from the roots of Clausena heptaphylla. The stems of another Clausena species, C. anisata Willd., contain atanisatin (1), and the roots contain a second new alkaloid, clausanitin (2).  

Non-isoprenoid Tryptamines.—The tryptamide (6) of an aminoethylthiazole carboxylic acid has been isolated from a Thermoactinomyces species (strain TM-64). 

Suzuki, S. Omura, and M. Onda, Chem. and Pharm. Bull. (Japan), 1976, 24, 92. 

Reagents i, MeCONMej, LiNPr, THF, -78 C ii, LiAlH4-THF-dioxan iii, HBr iv, KaFefCN), NaHCOa, HjO. 

In the /3-carboline series the tetrahydro-/3-carboline carboxylic acid (9) has been isolated from the seeds of Aleurites fordii Hemsl. This is the first reported 

Non-tryptamines.—The structure (1) of a new bromo-indole derivative, isolated from an Australian sponge of the genus Iotrocha, has been elucidated and confirmed by synthesis.4 The indole-3-acetic ester of myo-inositol occurs in rice kernels (Oryza sativa) 5a this is the first reported occurrence of this ester in a plant other than maize (Zea mays). 

Carbazomycins A and B, isolated from an unidentified Streptomyces species, prove to be the first known antibiotics that contain a carbazole skeleton. Carbazomycin B is 4-hydroxy-3-methoxy-l,2-dimethylcarbazole and carbazo-mycin A is its 0-methyl ether.5  

The structures of several carbazoles and pyranocarbazoles have been confirmed by synthesis these include lansine [2-hydroxy-3-formyl-6-methoxycarbazole - a 

Alkaloid Chemistry , Wiley—Interscience, New York, 1981. 

3 Indole and Biogenetically Related Alkaloids , ed. J. D. Phillipson and M. H. Zenk, Academic Press, New York, 1980. 

Non-tryptamines.— The stem bark of Murraya exotica L. [M. paniculata (L.) Jack.] contains mahanimbine and murrayazoline, and the leaves contain a new carbazole alkaloid, exozoline (1), which proves to be dihydrocyclomahanimbine it is of some interest that this plant has been examined on several previous occasions, but this is the first report of the presence of alkaloids in any of the tissues. 

The overall structure (2a) deduced for epicorazine A has been confirmed, and stereochemical detail has been added, by X-ray diffraction measurements. Its isomer, epicorazine B, which also occurs in Epicoccum nigrum, is simply the C-6 epimer (2b). The absolute configuration of epicorazine A follows from the 

The first naturally occurring indole N-glycoside has been encountered in neosidomycin, an antibiotic constituent of Streptomyces hygroscopicusf its structure (3) is also unique in that it is the only natural product known so far to contain methyl 4-deoxy-riho-hexopyranuronate as the sugar component. However, the configuration (d or l) of this sugar unit is at present unknown. 

6-Bis(y,y-dimethylallyl)indole (4), a new indole derivative from natural sources, occurs in the stem bark of Uvaria elliotiana Engl, et Diels (family Annonaceae).  

Novel indole derivatives continue to be found in marine organisms those reported recently include dendrodoine (3), a cytotoxic thiadiazole derivative, which occurs in the tunicate Dendrodoa grossularia, from Brittany,4 and the keto-lactam (4), one of two lactams isolated from the Caribbean sponge Hali-chondria melanodocia.5 

Durgeat, M. Guyot, C. Brassy, and B. Bachet, Tetrahedron Lett., 1980, 21, 1457. 

The fungus Claviceps paspali Stevens et Hall elaborates a series of metabolites derived from indole and a diterpenoid unit. The structures of paspaline (5) and paspalicine (6) were proposed earlier, together with the partial stereochemistry of paspaline. These conclusions have now been confirmed, and the complete stereochemistry of paspaline and paspalicine has been elucidated, by X-ray 

Bisdethiobis(methylthio)gliotoxin (lib) is an amorphous minor metabolite of Gliocladium deliquescens the structure (lib) was confirmed by its formation from gliotoxin, by methylation and reduction (MeI-MeOH-NaBH4).12b 

Gramodendrine (3) is a new, dipiperidylindole alkaloid which occurs in the aerial parts of Lupinus arbustus ssp. calcaratus. 

Its structure was deduced from spectral data, and confirmed by a simple Mannich synthesis from indole, formaldehyde, and ammo-dendrine.  

The antiepileptic alkaloid pimprinine (4), which was initially isolated from Streptomyces pimprina, has now been shown to be a metabolite of StreptoverticiIlium olivoreticuli (Arai, Nakada et 

Suzuki) Baldacci, Farina et Locci, ISP 5105, together with 

Streptomyces cinnamomeus. All three metabolites have been 

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Thomas (23) predicted that the non-tryptamine moiety of the indole alkaloids is derived from a cyclopentanoid monoterpene precursor. Wenkert (2k) independently reached to the same conclusion. 

Non-tryptamines.—Glycozoline (1) has been very simply synthesized by the thermal cyclization (350 °C) of 4 -methoxy-4-methyldiphenylamine in the presence of iodine.2 Details of the syntheses of girinimbine and mahanimbine have now been published,3 and the method used in the synthesis of the latter has been extended to the synthesis of ( )-isomahanimbine (2) thus, condensation of 2-hydroxy-6-methylcarbazole with citral in pyridine containing a trace of benzoic acid gave... 

Takano et al. have reported the first synthesis of ( )-antirhine (71) (Scheme 11),51 in which the problem of generating the desired, less stable (anti) stereochemistry at C-3 and C-15 was overcome by preparing the non-tryptamine fragment (72) from ( )-trinorcamphor (73) via a sequence of stereospecific reactions. Condensation of (72) with tryptamine, followed by cyclization and... 

Researches carried out to the early part of 1966 have been comprehensively reviewed and the present account will set out from that point. In brief, the situation reached at that time was as follows. Despite their bewildering variety, three main groups of alkaloids had been recognised (a) the Corynanthe-Strychnos type, e.g. ajmalicine (1) and akuammicine (2) which possess the non-tryptamine unit (3), (b) the Aspidosperma type, e.g. vindoline (4), in which the non-tryptamine unit appears as (5), and (c) the Iboga type, e.g. catharanthine (6), having still a different arrangement of the non-tryptamine unit (7). 

Non-tryptamines.—The number of carbazole derivatives isolated from the Rutaceae is now fourteen. Besides the tricyclic compounds murrayanine " (3-formyl-l-methoxycarbazole), glycozoline " (3-methoxy-6-methylcarbazole), glycozolidine " (2,4-dimethoxy-6-methylcarbazole), and (from Clausena hepta-phylla) heptaphylline (1), tetra- and penta-cyclic carbazoles have been obtained from Murraya koenigU3 ... 

Non-tryptamines.—In the Murray a carbazoles area, more details2 of the structural work on murrayacine1" (la) have been given. The alkaloid isomahanimbine1" (lb) has unfortunately been given a second name, mahanimbicine, in an independent structure determination.3 The hexacyclic bicyclomahanimbicine was also isolated in this investigation 3 it is related to the tetracyclic mahanimbicine ( = isomahanimbine) as bicyclomahanimbine is1" to mahanimbine, and can likewise be obtained from the tetracyclic compound by acid treatment... 

Non-tryptamines.—Details of the synthesis of 6-(3-methylbuta-l,3-dienyl)indole, a constituent of Monodora tenuifolia, have been published the same paper also records the synthesis of 6-(3-methyl-2-butenyl)indole, one of two indole alkaloids of Riccardia sinuata. " ... 

Non-tryptamines.—Details have been given of the 2T-ray analysis of dibromo-cannabicyclol which led to the revision of the structures of bicyclomahanimbine and bicyclomahanimbicine. Crombie and Whiting have also reported" that treatment of ( )-mahanimbine (40) with an acidic ion-exchange resin converts it into ( )-cyclomahanimbine (41) (Scheme 1) further spectral data are presented" for this structure. It seems likely" that curryanin" and murray-azolidine,"" both of which had been formulated as (42), actually have the structure (41). Further evidence for this revised structure for murrayazolidine ( =... 

Non-tryptamines.—The simple indoles in barley and tomato shoots have been identifiedamongst others, 3-formylindole, 5-hydroxytryptamine, and of course indole-3-acetic acid were common to both only barley had 3-aminomethyl- and 3-methylaminomethyl-indoles, gramine, iV -methyltryptamine, and 5-hydroxy-A(,-methyltryptamine. The seeds of Monodora tenuifolia, which are used to flavour food in West Africa, contain 6-(3-methylbuta-l,3-dienyl)indole. 

Monoterpenoid Alkaloids. — Corynantheine - Heteroyohimbine - Yohimbine Group, and Related Oxindoles. Details of the AT-ray crystal structure determination of borreline (92) have now been published,and the species from which it was isolated has been identified as Borreria capitata R. et P. A second alkaloid from this species, borrecapine (93), has a similar structure but, in place of the second methyl group in borreline, borrecapine contains an isobutenyl group which completes the monoterpenoid unit of the non-tryptamine part of the molecule. 

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