Exploration of the enantioselective Birch-Cope sequence for the synthesis of carbocyclic quaternary stereocenters.
Quaternary stereocenters on a 2-cyclohexen-1-one ring are synthesized with good to excellent levels of enantioselectivity. The quaternary stereocenter is created through a new synthetic sequence involving three reactions: the enantioselective Birch reduction-allylation, enol ether hydrolysis, and the Cope rearrangement. To illustrate the ability of the sequence to enantioselectively generate complex structures, a variety of substrates are described. Notably, the sequence works for the enantioselective generation of vicinal quaternary-tertiary stereocenters, the generation of congested arylic quaternary stereocenters, and hydroxyalkyl substituted quaternary stereocenters.
Paul
Tapas
T
Department of Chemistry, Bryn Mawr College, Bryn Mawr, Pennsylvania 19010-2899, USA.
Malachowski
William P
WP
Lee
Jisun
J
D003512:Cyclohexanones / Q000737:chemistry*; D053138:Cyclohexenes / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis*; D006900:Hydroxylation; D008956:Models, Chemical; D013237:Stereoisomerism
D003512:Cyclohexanones; D053138:Cyclohexenes; D006844:Hydrocarbons, Cyclic