All's well that ends well! The complete assignment of the structure of the largest known natural product that is not a biopolymer (maitotoxin) has concluded with the determination of the configurations of the stereogenic centers in its two acyclic side chains. The results of NMR studies were confirmed by comparison with synthesized model compounds. The absolute configuration was determined by analysis of a fragment of the natural product and a corresponding synthesized unit by GC with a chiral column. In the contracted structure below, the acyclic side chains are attached to the termini of a polycyclic polyether.
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Nonomura et al. (1996) studied this question.
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