Asymmetric synthesis of functionalized cyclohexanes bearing five stereocenters via a one-pot organocatalytic Michael-Michael-1,2-addition sequenceElectronic supplementary information (ESI) available. CCDC 990847. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc01885k

A highly stereoselective one-pot procedure involving an enantioselective Michael addition promoted by low loading of an amino-squaramide catalyst followed by an achiral base catalyzed domino Michael-Knoevenagel-type 1,2-addition sequence provides efficient access to fully substituted cyclohexanes bearing five contiguous stereogenic centers in good yields (68-86%) and excellent stereoselectivities (>30 : 1 dr and 96-99% ee). A highly stereoselective one-pot organocatalytic procedure involving a Michael-Michael-1,2-addition sequence provides an efficient access to fully substituted cyclohexanes bearing five contiguous stereocenters in good yields and excellent stereoselectivities.