Stylissadines A and B: the first tetrameric pyrrole-imidazole alkaloids.

[reaction: see text] Pyrrole-imidazole alkaloids are widely distributed in marine sponges of the orders Halichondrida and Agelasida. Chemical investigation of the Caribbean sponge Stylissa caribica led to the isolation of the first tetrameric pyrrole-imidazole alkaloids. The so-called stylissadines are the largest and most complex pyrrole-imidazole alkaloids discovered so far and are therefore a major challenge for the structure determination by NMR spectroscopy. Their isolation and structure elucidation are discussed in detail.