Chiral Auxiliary Approach for Gold(I)-Catalyzed Cyclizations

Identifier:  imarina:9331756

Handle: https://hdl.handle.net/20.500.11797/imarina9331756

Authors:  Cataffo, Andrea; Pena-Lopez, Miguel; Pedrazzani, Riccardo; Echavarren, Antonio M

Abstract:
Two different classes of stereoselective cyclizations have been developed using a chiral auxiliary approach with commercially available [JohnPhosAu(MeCN)SbF6] as catalyst. First, a stereoselective cascade cyclization of 1,5-enynes was achieved using the Oppolzer camphorsultam as chiral auxiliary. In this case, a one-pot cyclization-hydrolysis sequence was developed to directly afford enantioenriched spirocyclic ketones. Then, the stereoselective alkoxycyclization of 1,6-enynes was mediated by an Evans-type oxazolidinone. A reduction-hydrolysis sequence was selected to remove the auxiliary to give enantioenriched β-tetralones. DFT studies confirmed that the steric clash between the chiral auxiliary and alkene accounts for the experimentally observed diastereoselective cyclization through the Si face.