The structure 3,4-dihydroxy-2,4,6,8-tetramethyldec-8-enolide (1) was assigned to a metabolite of Botrytis cinerea, but the spectra of several synthetic analogues had significant differences from that of 1. Examination of the constituents of a B. cinerea mutant that overproduces polyketides gave sufficient quantities of 1, now named cinbotolide, for chemical transformations. These led to a revised γ-butyrolactone structure for the metabolite. This structure has been confirmed by an asymmetric total synthesis, which also established its absolute configuration.
The asymmetric synthesis of the antibacterial and antitumoral natural compound xylariolide A (1) and five stereoisomers has been achieved. The strategy is based on the one‐pot epoxidation/lactonisation or dihydroxylation/lactonisation of the hypothetical biosynthetic intermediate xylarioic A acid (8). The absolute configuration of xylariolide A was thus determined to be 3R,4S,5R,1′R,2′R after the synthesis of 1, two epimers, i.e., 1′‐epi‐xylariolide A (3) and 2′‐epi‐xylariolide A (4), and three more diastereoisomers 5–7.
The asymmetric synthesis of key fragments of the phytotoxic toxins botcinolide/botcinin is reported. The synthesis of 1 and 1a are based on a convergent route via esterification and alkene metathesis of fragments A, B or C, B, which were obtained by Evans aldol condensation and stereoselective crotylation, respectively.
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