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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
A reductive-coupling plus Nazarov cyclization sequence in the asymmetric synthesis of five-membered carbocycles
Daniel J Kerr1, Jonathan M White, Bernard L Flynn
1Medicinal Chemistry and Drug Action, Monash Institute of Pharmaceutical Sciences, Monash University, 381 Royal Parade, Parkville Vic 3052, Australia.
Abstract:
Palladium-mediated hydrostannylation of alkynoyl compounds is combined with Stille-Scott cross-coupling (reductive-coupling) to give one-pot access to divinyl and aryl vinyl ketones, which undergo Nazarov cyclization to give cyclopentenones upon treatment with acid. This reaction sequence has been studied with a variety of different substitution patterns, including the use of oxazolidinone auxiliaries to achieve torquoselectivity in the Nazarov cyclization. Through a combination of good yields and moderate to good levels of stereochemical induction, this approach affords efficient, convergent, and asymmetric access to a variety of different cyclopentanoid systems.
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