Work

Sm-Catalyzed Reductive Transformations of Enones

Year: 2026

Type: preprint

Abstract: We report two Sm-catalyzed reductive transformations of enones. Using catalytic Sm(OTf)3 and Zn0 as the terminal reductant, Wieland–Miescher-type ketones underwent ring contraction to trans-hydrindanes bearing vicinal quaternary stereogenic centers. Under similar conditions but with 2-naphthalenethiol as a hydrogen atom donor, diastereoselective enone reduction outcompeted the ring contraction pathway, furnishing decalin products. The diastereoselectivity of the enone reduction was shown to be controlled primarily by the substrate structure; however, for certain substrates, the thiol structure could be used to improve the diastereoselectivity. Mechanistic investigation by cyclic voltammetry is also reported.

Source: ChemRxiv

DOI: 10.26434/chemrxiv.15010939/v1

Authors: Nathan C. Friede, Kristen E. Gardner, Nhu H. Quach, Matthew Neurock, Sarah E. Reisman

Institutions: California Institute of Technology, University of Minnesota

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, California Institute of Technology, University of Minnesota, Division of Chemistry

Awards: G3461526233, Postdoctoral Fellowship: MPS-Ascend: Development of Ni-catalyzed Asymmetric Cross-Coupling of Unactivated C(sp3) Electrophiles Using a Dual Catalysis System, G4672175627, Center: NSF Center for Synthetic Organic Electrochemistry, Graduate Research Fellowship Program (GRFP)

OpenAlex ID: W7223291918

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