Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

Allen Y. Hong, Nathan B. Bennett, Michael R. Krout, Thomas Jensen, Andrew M. Harned, Brian M. Stoltz

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.
Original languageEnglish (US)
Pages (from-to)10234-10248
Number of pages15
JournalTetrahedron
Volume67
Issue number52
DOIs
StatePublished - Dec 2011
Externally publishedYes

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