Synthesis of 1,3,4,5-tetrahydropyrrolo-[4,3,2-de]quinolines via the vicarious nucleophilic sybstitution of hydrogen

Mąkosza, Mieczysław; Stalewski, Jacek

doi:10.1016/0040-4020(95)00350-h

Cited by 23 publications

(8 citation statements)

References 15 publications

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“…We have been developing 27,28 an alternative strategy, namely the construction of such molecules starting from a quinoline; recently two other groups have also described approaches to these tricycles from quinoline or reduced quinoline intermediates 29,30 and one of these was taken through to dehydrobufotenine, damirones A and B, and makaluvamine C. 29 Scheme 1 summarizes our strategy, showing the development of a 4-methylquinoline A into a 5-amino-1,2,3,4-tetrahydroquinoline-4-aldehyde B in which closure of the pyrrole ring produces target tricycle C. We have detailed 27 syntheses of 8-methoxy-1,3,4,5tetrahydropyrrolo[4,3,2-de]quinoline starting from a simple quinoline, 6-methoxy-4-methylquinoline. This paper describes our further work in this area, some of which has been published in preliminary form, 28 which constitutes formal total syntheses of damirones A, 2a, and B, 2b, batzelline C, 2c, isobatzelline C, 3a, makaluvamines A-D, 3b-e, respectively, and discorhabdin C, 4.…”

Section: Introductionmentioning

confidence: 99%

“…We have been developing , an alternative strategy, namely the construction of such molecules starting from a quinoline ; recently two other groups have also described approaches to these tricycles from quinoline or reduced quinoline intermediates , and one of these was taken through to dehydrobufotenine, damirones A and B, and makaluvamine C . Scheme summarizes our strategy, showing the development of a 4-methylquinoline A into a 5-amino-1,2,3,4-tetrahydroquinoline-4-aldehyde B in which closure of the pyrrole ring produces target tricycle C .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Pyrrolo[4,3,2-de]quinolines from 6,7-Dimethoxy-4-methylquinoline. Formal Total Syntheses of Damirones A and B, Batzelline C, Isobatzelline C, Discorhabdin C, and Makaluvamines A−D

Roberts¹,

Joule²,

Ma³

et al. 1997

J. Org. Chem.

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2-Amino-4-nitrophenol and 2-methoxy-5-nitroaniline were converted into the 5-nitroquinolines 6b and 6d, respectively, and then the latter into nitro-acetal 6f. 6,7-Dimethoxy-4-methylquinoline (6g) was nitrated at C-5 and then the methyl substituent converted into aldehyde 6j and then protected giving acetal 6l. Various means, notably a large excess of NiCl(2)/NaBH(4), were used to reduce both nitro group and pyridine ring, forming 1,2,3,4-tetrahydroquinolines such as 7b, 7c, 7d, which under acidic conditions closed to give 1,3,4,5-tetrahydropyrrolo[4,3,2-de]quinolines 9a, 9d, 9c, respectively. In some cases it was unnecessary to protect the aldehyde function, for example quinolinium salt 12c gave 9j and nitro-aldehyde 6j gave 9e (after BOC protection) directly by reaction with NiCl(2)/NaBH(4). Substitution of the indole and aniline nitrogens in the 1,3,4,5-tetrahydropyrrolo[4,3,2-de]quinolines was based on a combination of protection, selective deprotection, and the exploitation of the greater acidity of the indole N-hydrogen. 8-Chlorination of 6h and then conversions, as above, gave chloro-diamine-acetal 7e which on acid treatment produced iminoquinone 11b; formylation of the nitrogens in 7e and then acidic treatment allowed formation of the chlorine-substituted 1,3,4,5-tetrahydropyrrolo[4,3,2-de]quinoline 9m which was then converted into 9p. De-O-methylation and then oxidation of 9b and 9c gave o-quinones 10b and 10a, respectively.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Pyrrolo[4,3,2-de]quinolines from 6,7-Dimethoxy-4-methylquinoline. Formal Total Syntheses of Damirones A and B, Batzelline C, Isobatzelline C, Discorhabdin C, and Makaluvamines A−D

Roberts¹,

Joule²,

Ma³

et al. 1997

J. Org. Chem.

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“…In most syntheses, the tricyclic heterocycle has been formed from a preexisting indole. The six-membered ring is then closed by condensation of a tryptamine quinone or cyclization of a 4-aminoindole bearing a two-carbon chain at the 3-position. − Examples include the syntheses of unsubstituted 12 and 1-methyl-substituted 13 tricyclic systems of O -methylnordehydrobufotenine, dehydrobufotenine, damirones A and B,11a makaluvamines, batzelline C and isobatzelline C, and discorbhadin C. 11b,16b,c, …”

Section: Introductionmentioning

confidence: 99%

Novel Syntheses of Tetrahydropyrroloquinolines: Applications to Alkaloid Synthesis

1996

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Two novel routes involving the intramolecular olefin insertion with a zirconium−benzyne complex, followed by a palladium-catalyzed aryl amination, have been developed for the synthesis of tetrahydropyrroloquinolines. In one approach, exemplified in the six-step total synthesis of the South American toad poison dehydrobufotenine (1), the tricyclic system was formed via the Pd-catalyzed ring closure of a functionalized tryptamine derivative. In the second, cyclization of an appropriately substituted quinoline yields 13, an intermediate in the synthesis of damirones A and B, and also makaluvamine C, a topoisomerase II inhibitor exhibiting antitumor properties.

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“…can be readily converted into benzisoxazoles (anthraniles) via treatment with Me,SiCl/triethylamine (26) or, in the case of bicyclic system, via a reaction with some nucleophilic agents (27). O-Methylnordehydrobufotenine can be efficiently synthesized from 2-nitro-5-bromoanisole via the VNS cyanomethylation followed by standard transformations (28). The rich possibilities of heterocyclic ring synthesis presented in this paper are far from being exhausted.…”

Section: Ohmentioning

confidence: 96%

Synthesis of heterocyclic compounds via vicarious nucleophilic substitution of hydrogen

Makosza¹

1997

Pure and Applied Chemistry

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Synthesis of 1,3,4,5-tetrahydropyrrolo-[4,3,2-de]quinolines via the vicarious nucleophilic sybstitution of hydrogen

Cited by 23 publications

References 15 publications

Synthesis of Pyrrolo[4,3,2-de]quinolines from 6,7-Dimethoxy-4-methylquinoline. Formal Total Syntheses of Damirones A and B, Batzelline C, Isobatzelline C, Discorhabdin C, and Makaluvamines A−D

Synthesis of Pyrrolo[4,3,2-de]quinolines from 6,7-Dimethoxy-4-methylquinoline. Formal Total Syntheses of Damirones A and B, Batzelline C, Isobatzelline C, Discorhabdin C, and Makaluvamines A−D

Novel Syntheses of Tetrahydropyrroloquinolines: Applications to Alkaloid Synthesis

Synthesis of heterocyclic compounds via vicarious nucleophilic substitution of hydrogen

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