jo9b03221_si_001.pdf (1.24 MB)
Structure Revisions of the Sponge-Derived Dibrominated Bis-indole Alkaloids, Echinosulfone A and the Echinosulfonic Acids A to D
journal contribution
posted on 2020-02-21, 21:31 authored by Darren
C. Holland, Milton J. Kiefel, Anthony R. CarrollThe structures of the sponge-derived
dibrominated bis-indole alkaloids,
namely, echinosulfone A (2) and the echinosulfonic acids
A to D (9–12), have been revised
based upon reanalysis of their NMR spectroscopic and MS spectrometric
data, comparison of this data with those reported for structurally
related compounds, and based on their common biogenesis. The reinterpreted
spectroscopic evidence has been corroborated by the total synthesis
of the revised structure of echinosulfone A (2). This
was achieved by bis-carbonylation at C-3 of the magnesium salt of
6-bromoindole with triphosgene to afford the new dibrominated bis-indole
ketone, bis(6-bromo-1H-indol-3-yl)methanone (3), followed by N-sulfonation of one indole moiety to furnish
6-bromo-3-(6-bromo-1H-indole-3-carbonyl)-1H-indole-1-sulfonate (2). The five marine alkaloids
corrected herein each contain an indole sulfamate and are all carbon-bridged
dibrominated bis-indoles: echinosulfone A (2) is a di(1H-indol-3-yl)methanone, while the echinosulfonic acids A
to D (9–12) are methyl 2,2-bis(1H-indol-3-yl) acetates.