Banwell, MartinJackson, KerrieWillis, Anthony2015-12-070040-4020http://hdl.handle.net/1885/25711Total syntheses of title natural products, 1 and 2, have been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered micro-organism Escherichia coli JM109 (pDTG601) that over-expresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in these syntheses, the first of which was a high-pressure-promoted Diels-Alder cycloaddition reaction between diene 8 and cyclopentenone to give adduct 9. The second key step was the photochemically promoted oxa-di-π-methane rearrangement of the bicyclo[2.2.2]octenone derivative, 18, of 9 to give 20 while the third key step was the reductive cleavage of the last compound so as to afford the linear triquinane 22. Elaboration of compound 22 to targets 1 and 2 followed conventional and/or established procedures. Single-crystal X-ray analyses were carried out on compounds 10-13, 15, 18, 24, and 34.Keywords: bicyclo compound; catechol derivative; complicatic acid; cyclopentenone; dioxygenase; hirsutic acid; methane; natural product; toluene; toluene dioxygenase; unclassified drug; article; biotransformation; crystal structure; cycloaddition; Diels Alder react (+)-Hirsutic acid; (-)-Complicatic acid; Chemoenzymatic; cis-1,2-Dihydrocatechol; Diels-Alder reaction; Oxa-di-p-methane rearrangement; Sesquiterpene; Triquinane200710.1016/j.tet.2007.03.0732015-12-07