Rearranged caryophyllenes by biotransformation with Chaetomium cochliodes

Biotransformation of caryophyllene by Chaetomium cochliodes DSM 1909 (=ATCC 10195) leads to 4,5-epoxy-caryophyllene-7,12-diol as the main product. The hydroxylation of the geminal methyl groups is not very stereospecific, but as with Diploida gossypina the main product possesses the 11R-configuration. Side-reactions are ring contraction or formation of clovanes, probably via epoxide rearrangements. The use of mono- or diepoxy-caryophyllene as the substrate does not increase the yields significantly. Instead, diepoxy-caryophyllene gave a punctatin derivative. The same molecular framework, but with a different configuration, was observed among the fermentation products from Diplodia gossypina, which supports the assumption that a caryophyllane is the precursor of this class of antibiotics.