The basic research described in this proposal concerns studies in fundamental organic chemistry in the field of organocatalysis. Despite the considerable progresses of the science of organic synthesis and the advent of organocatalysis, general methods to generate chiral “all carbon” quaternary centers with high levels of stereoselectivity are rare, and this synthetic issue remains a challenge. Chiral “all carbon” quaternary centers can be found in spiro bicyclic compounds, a class of molecules with spectacular chemical and conformational properties. We propose to develop a general and flexible stereoselective organocatalytic approach to spiro compounds containing a chiral “all carbon” spiro carbon atom using the reactivity of zwitterionic ketoenolate equivalents mediated by Lewis base catalysts (NHCs and isothioureas). We also propose to develop a new class of organocatalysts for iminium activation with enhanced catalytic activity and stereoselectivity when compared to state of the art organocatalysts. These new organocatalysts have been rationally designed around a conformationally constraint spiro bicyclic core containing a chiral “all carbon” spiro carbon atom, and they may be prepared by the method we propose to develop using the reactivity of zwitterionic ketoenolate equivalents. We anticipate that our designed organocatalysts for iminium activation will allow for unprecedentedly efficient and stereoselective reactions, more specifically for the preparation of molecules with chiral “all carbon” quaternary centers.