Abstract Stigmatellin A (1) isolated from the myxobacterium Stigmatella aurantiaca is a powerful inhibitor of electron transport in mitochondria and chloroplasts. The first highly diastereo-and enantioselective total synthesis of this important natural product is described. Key steps in the synthesis are the alkylation of the SAMP-hydrazone (S)-13, a titanium mediated syn-diastereoselective aldol reaction, the anti-diastereoselective ...