Myrmicarin 430A: a new heptacyclic alkaloid from Myrmicaria ants

Chem. Commun.
2004.0

Abstract

Myrmicarin 430A, the major C30N2 alkaloid from the poison gland secretion of African Myrmicaria opaciventris ants, is a heptacyclic alkaloid with an entirely new carbon skeleton composed of two unbranched C15 chains. Myrmicine ants produce diverse alkaloids (e.g., pyrrolidines, piperidines, pyrrolizidines, indolizidines) with biological functions and pharmacological interest, most of which have unbranched carbon chains derived from the acetate pool. Due to its extreme sensitivity (over 90% decomposition after 1 hour in air at ambient temperature), myrmicarin 430A could not be isolated, so NMR analysis was performed on unpurified extracts of 30 freshly dissected poison glands immediately after preparation. Using phase-sensitive (1H,1H)-DQ-COSY, sensitivity-enhanced HSQC with gradients, and HMBC experiments, its structure was elucidated: it contains a hexahydropyrrolo[2,1,5c,d]indolizine subunit (spin system I) and another subunit with spin systems II/III and a second nitrogen, forming a heptacyclic structure with two enamine double bonds. GC-MS analysis revealed two alkaloid groups (C15N: myrmicarin 215A/B/217; C30N2: myrmicarin 430A) and monoterpene hydrocarbons. In conclusion, myrmicarin 430A represents a novel heptacyclic alkaloid structure, among the most complex identified in ants.

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