Catalytically Generated Vanadium Enolates Formed via Interruption of the Meyer-Schuster Rearrangement as Useful Reactive Intermediates

Accounts of Chemical Research
Barry M Trost, Jacob S Tracy

Abstract

ConspectusEnolate chemistry is one of the most fundamental strategies for the formation of carbon-carbon and carbon-heteroatom bonds. Classically, this has been accomplished through the use of stoichiometric quantities of strong base and cryogenic reaction temperatures. However, these techniques present issues related to enolate regioselectivity and functional group tolerance. While more modern methods utilizing stoichiometric activating agents have overcome some of these limitations, these processes add additional steps and suffer from poor atom economy. While certain classes of highly acidic nucleophiles have enabled the development of elegant and general catalytic solutions to address all of these limitations, functionalizing less acidic nucleophiles remains difficult.To overcome these challenges, we developed an alternative general approach for the formation and subsequent functionalization of metal enolates that leverages catalytic amounts of Lewis acid and entirely avoids the need for exogenous base or stoichiometric additives. To do so, we re-engineered the classical Meyer-Schuster rearrangement, which normally converts propargylic alcohols into α,β-unsaturated carbonyl compounds. By careful control of reaction condition...Continue Reading

References

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