Alkaloids from a panamanian poison frog, Dendrobates speciosus: identification of pumiliotoxin-A and allopumiliotoxin class alkaloids, 3,5-disubstituted indolizidines, 5-substituted 8-methylindolizidines, and a 2-methyl-6-nonyl-4-hydroxypiperidine.
Dendrobates speciosus is a small red or orange frog that occupies a small geographic range in the highlands of western Panama, where it occurs abundantly in some cloud forest habitats. Gc-ms analysis indicated the presence of at least 30 alkaloids in MeOH skin extracts from population samples at the extreme eastern end of the known geographic range. Eleven alkaloids were isolated by cc in quantities sufficient for 2D-nmr spectral analysis, which in some cases confirmed their identity with alkaloids known from other species and in other cases led to assignment of structures. Pumiliotoxin 251D, pumiliotoxin A [307A], pumiliotoxin B [323A], and allopumiliotoxin 267A were identified as major constituents. N-Oxides of 323A and 267A were also isolated. Indolizidines 195B and 223AB with 3-butyl-5-methyl and 3-butyl-5-propyl substituents, respectively, were identified. The 5-substituents of the 8-methyl-indolizidines 207A and 235B' were assigned as -(CH2)3CH = CH2 and -(CH2)5CH = CH2, respectively; indolizidine 235B' from D. speciosus is, thus, a positional double-bond isomer of indolizidine 235B previously isolated from a closely related poison frog, Dendrobates pumilio. A piperidine 241D was isolated and assigned the structure cis-cis-2-methyl-6-nonyl-4-hydroxypiperidine.
Edwards
M W
MW
Laboratory of Bioorganic Chemistry, National Institute of Diabetes and Digestive and Kidney Diseases, Bethesda, Maryland 20892.
Daly
J W
JW
Myers
C W
CW
D000470:Alkaloids / Q000145:classification / Q000302:isolation & purification*; D000664:Amphibian Venoms / Q000145:classification / Q000302:isolation & purification*; D000818:Animals; D001001:Anura; D007211:Indoles / Q000302:isolation & purification; D007212:Indolizines; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010880:Piperidines / Q000302:isolation & purification
D000470:Alkaloids; D000664:Amphibian Venoms; D007211:Indoles; D007212:Indolizines; D010880:Piperidines; C035482:pumiliotoxin A; C007948:histrionicotoxin