Yan, QiaoBolte, BenoitBai, YuhuaBanwell, MartinWillis, AnthonyCarr, Paul D2019-04-080022-3263http://hdl.handle.net/1885/159303A series of enantiomerically pure bicyclo[2.2.2]octenones, including the lactone-annulated system 26, has been prepared by engaging derivatives of an enzymatically derived and homochiral cis-1,2-dihydrocatechol in inter- or intra-molecular Diels–Alder reactions. Systems such as 26 readily participate in photochemically promoted oxa-di-π-methane rearrangement or 1,3-acyl migration processes to give products such as diquinane 34 or mixtures of cyclobutanone 36 and cyclopropane 38, respectively.We thank the Australian Research Council and the Institute of Advanced Studies for financial support. Q.Y. is the grateful recipient of a CSC PhD Scholarship provided by the Government of the People’s Republic of China.application/pdfen-AU© 2017 American Chemical Society201710.1021/acs.joc.7b012432019-03-12