The detoxin complex is a group of depsipeptide metabolites produced by the organism Streptomyces caespitosus var. detoxicus 7072 GC1 as well as other strains of Streptomyces. The complex is the first isolated natural product which displays a unique detoxification effect in plant and animal cells as its biological activity. The structural investigations carried out to elucidate the structures of the congeners and the stereochemistry of the stereogenic centers are described. Structure-activity relationships are discussed. The different synthetic approaches to the parent amino acid, (-)detoxinine, are compared. The syntheses of detoxins (-)-B1, (-)-B3, (-)-D1, and(+)-valyldetoxinine are described.