Shockley, Samantha E. Holder, Jeffrey C. Stoltz, Brian M. A Catalytic, Enantioselective Formal Synthesis of (+)-Dichroanone and (+)-Taiwaniaquinone H A catalytic, enantioselective formal synthesis of (+)-dichroanone and (+)-taiwaniaquinone H is reported. The all-carbon quaternary stereocenter was constructed by asymmetric conjugate addition catalyzed by a palladium­(II) (S)-<i>tert</i>-butyl­pyridino­oxazoline complex. The unexpected formation of a [3.2.1] bicyclic intermediate required the identification of a new route. Analysis of the Hammett constants for <i>para</i>-substituted arenes enabled the rational design of a highly enantioselective conjugate addition substrate that led to the completion of the formal synthesis. Catalytic;bicyclic;stereocenter;Enantioselective Formal Synthesis;enantioselective conjugate addition substrate;HA;taiwaniaquinone;completion;Dichroanone;identification;synthesis;conjugate addition;dichroanone;formation;palladium;arene;Hammett constants;analysis;quaternary;Taiwaniaquinone 2015-12-17
    https://acs.figshare.com/articles/dataset/A_Catalytic_Enantioselective_Formal_Synthesis_of_Dichroanone_and_Taiwaniaquinone_H/2045940
10.1021/ol5031537.s002