(-)-Temuconine, a New Bisbenzylisoquinoline Alkaloid from Aristolochia elegans

Journal of Natural Products
1989.0

Abstract

Aristolorhia elegam of Egyptian origin has yielded the new bisbenzylisoquinoline (-)-temuconine [1], which is enantiomeric with the previously described (+)-temuconine obtained from Chilean Berberis valdiviana. In a continuation of our investigation on the alkaloidal constituents of Aristolochia elegans Mast. (Aristolochiaceae) (1), we wish to describe the new bisbenzylisoquinoline (-)-temuconine [1], C37H42N2O6. This dimer suffered facile mass spectral fragmentation to supply the weak ion m/z [M-1]+. The base peak, m/z 206, represented rings A' and B'. Another very strong peak was m/z 192 due to rings A and B. This cleavage pattern is typical of bisbenzylisoquinolines of subgroup A (11-12'), which incorporate only tail-to-tail coupling (2). The ¹H-nmr spectrum of (-)-temuconine (CDCl3, 500 MHz) was also characteristic of subgroup A (3) and has been summarized around structure 1. Two N-methyl singlets are in evidence at δ 2.46 and 2.52. Three methoxyls are also present, indicated by signals at δ 3.65, 3.82, and 3.85; as well as eleven aromatic protons with signals stretched between δ 6.30 and 7.10. All of these chemical shifts matched those previously reported for (+)-temuconine found in Berberis valdiviana (Berberidaceae) (4) and so indeed did the mass spectrum. Nevertheless, the strong negative specific rotation of our (-)-temuconine [1] indicated that we had on hand the enantiomer of the previously described dextrorotatory isomer. The cd spectrum of our (-)-temuconine [1] exhibited troughs at 287 and 223 nm, pointing to the 1S, 1'R configuration, as indicated in expression 1(5). It is worth noting that we have here a rare instance in which enantiomeric bisbenzylisoquinolines have been recognized. But it still remains true that to date no bisbenzylisoquinolines have been isolated from nature as racemates.

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