An e×peditious synthesis of (±)-decahydro-5&lt;i&gt;H&lt;/i&gt;-dipyrrolo [1,2-&lt;i&gt;a&lt;/i&gt;:1',2'-&lt;i&gt;c&lt;/i&gt;]pyrimidine-5-carbonitrile: a formal synthesis of (±)-tetraponerines-1, -2, -5, and -6

To evaluate the influences of the tetraponerine alkyl chains and tricyclic ring systems on their cytotoxic activities, we have prepared a series of alkyl derivatives (3a, 3b and 4a–f) of the non‐natural tricyclic skeletons decahydro‐2H,6H‐dipyrido[1,2‐a:1′,2′‐c]pyrimidine (3, 6–6–6 skeleton) and dodecahydro‐2H‐1,8a‐diazaphenanthrene (4, iso‐6–6–6 skeleton). In this study, two ways to synthesise the 6–6–6 analogues have been developed and compared. One is based on the condensation of α‐tripiperideine with diethyl malonate (DEM) in water at pH 11. This yielded oxo ester 11, precursor of the amino nitrile 8, but only in moderate yield. In the second pathway, the key intermediate 8 was more efficiently synthesised by starting from 2‐(2‐piperidyl)ethanol. Treatment of 8 with alkyl Grignard reagents led to the 6–6–6 analogues 3a and 3b. When the one‐pot reaction between α‐tripiperideine and DEM was performed in water at pH 8, the lactam 12, precursor of the iso‐6–6–6 skeleton, was obtained in a yield of 76 %. The same lactam was also obtained in a yield of 86 % by treatment of tetrahydroanabasine 14 with DEM in water at pH 8. Lactam 12 was transformed into the iso‐6–6–6 analogues 4a–4f. The cytotoxic activities of the 6–6–6 and iso‐6–6–6 analogues against HT29 cancer cells were compared with those of the 5–6–5 and 6–6–5 tetraponerines and with those of solenopsin analogues. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids. II. Tetraponerines from pseudomyrmecine ants

Garraffo¹,

Jain²,

Kaneko³

et al. 2001

Rapid Comm Mass Spectrometry

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Chemical ionization tandem mass spectrometry (CI-MS/MS) of alkaloids with ammonia reagent gas and collision-activated dissociation as well as EI-MS/MS were applied to the tetraponerine alkaloids in extracts from six pseudomyrmecine ants of the genus Tetraponera. The MS/MS techniques along with gas chromatography Fourier transform infrared (GC/FTIR) spectra allowed identification in two extracts of seven of the eight known tetraponerines. The EI-MS/MS fragmentations proved diagnostic for the ring system and the CI-MS/MS patterns for the C-8 or C-9 substitution, while the Bohlmann bands in FTIR spectra were diagnostic for the C-8 or C-9 configurations. An Indian ant (T. allaborans) had T-2, T-4 and T-8, while a Chinese ant (T. binghami) had T-5, T-6, T-7 and T-8. Four other ants, T. rufonigra (India), T. penzigi (Africa), T. clypeata (Africa) and T. sp. cf. emeryi (Africa), had no tetraponerines.

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An e×peditious synthesis of (±)-decahydro-5<i>H</i>-dipyrrolo [1,2-<i>a</i>:1',2'-<i>c</i>]pyrimidine-5-carbonitrile: a formal synthesis of (±)-tetraponerines-1, -2, -5, and -6

Cited by 4 publications

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ChemInform Abstract: An Expeditious Synthesis of (.+‐.)‐Decahydro‐5H‐dipyrrolo[1,2‐a:1′,2′‐c]pyrimidine‐5‐carbonitrile: A Formal Synthesis of (.+‐.)‐Tetraponerines‐1, ‐2, ‐5, and ‐6.

ChemInform Abstract: An Expeditious Synthesis of (.+‐.)‐Decahydro‐5H‐dipyrrolo[1,2‐a:1′,2′‐c]pyrimidine‐5‐carbonitrile: A Formal Synthesis of (.+‐.)‐Tetraponerines‐1, ‐2, ‐5, and ‐6.

Synthesis of New Analogues of the Tetraponerines

Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids. II. Tetraponerines from pseudomyrmecine ants

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