Palladium-catalyzed elimination reactions of stereodefined enol triflates

Date

2013

Authors

Crouch, Ian T.

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Abstract

The following dissertation will describe palladium-catalyzed reactions of stereodefined enol triflates, which are readily accessible from the corresponding ß-ketoesters. Both 2,4- dienoate esters and chiral allenic esters are highly referenced synthetic intermediates. Through manipulation of reaction conditions, a general procedure for obtaining 2,4-dienoate esters from either [Z]- or [E]- enol triflates is presented. Using a chiral palladium catalyst, a highly enantioselective synthesis of allenic esters is demonstrated, which is proposed to proceed through a mechanism involving enantioselective ß-hydride elimination. The development of novel chiral ligands for this purpose is put forth. This methodology is applied to a formal total synthesis of the natural product (+) epibatidine.

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Keywords

allene, beta-hydride, elimination, enantioselective, palladium, triflate

Citation

Department

Chemistry