An enantioselective organocatalytic intramolecular Morita-Baylis-Hillman (IMBH) reaction of dienones, and elaboration of the IMBH adducts to fluorenonesElectronic supplementary information (ESI) available. CCDC 1520308 and 1520613. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7cc02524f

An enantioselective organocatalytic intramolecular Morita-Baylis-Hillman (IMBH) reaction of dienones is reported for the first time. This has been achieved by incorporating entropy and synergy considerations during the substrate design. The reaction conditions are thoroughly verified for an efficient synthesis of highly functionalised cyclopenta-fused arenes and heteroarenes in excellent yields and enantioselectivities. The synthetic utility of the IMBH-adducts has been demonstrated by transforming them into 3,4-disubstituted fluorenones in a serendipitous manner. An efficient synthesis of cyclopenta-fused arenes and heteroarenes has been achieved via an enantioselective organocatalytic intramolecular Morita-Baylis-Hillman (IMBH) reaction of dienones. The IMBH-adducts were transformed to fluorenones in a serendipitous manner.