Palladium-Catalyzed Suzuki-Miyaura, Heck and Hydroarylation Reactions on (-)-Levoglucosenone and Application to the Synthesis of Chiral γ-Butyrolactones

Kieran P. Stockton, Christopher J. Merritt, Christopher J. Sumby, Ben W. Greatrex

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27 Citations (Scopus)

Abstract

The chiral pool material (-)-levoglucosenone (6,8-dioxabicyclo[3.2.1]oct-2-en-4-one, LGO) has been substituted by using a series of Pd-mediated cross-coupling reactions. Iodination of LGO followed by Suzuki-Miyaura cross-coupling reaction with boronic acids by employing the Buchwald ligand SPhos with Pd(OAc)2 afforded 3-aryl derivatives in excellent yields. Selective Heck arylation reaction at the 2-position was achieved with aryl iodides with K3PO4 as base and SPhos ligand with Pd(OAc)2 (1-5 mol-%). A selective hydroarylation reaction (formal conjugate addition) was developed by using the same aryl iodides, benzyldiethylamine, Pd(OAc)2, and P(o-tol)3. The products were converted, either directly or after alkene reduction, through a Baeyer-Villiger oxidation into chiral 3- and 4-substituted 5-(hydroxymethyl)dihydrofuran-2(3H)-ones. Three new cross-coupling approaches to the derivatization of levoglucosenone are described and the products converted into butyrolactones.

Original languageEnglish
Pages (from-to)6999-7008
Number of pages9
JournalEuropean Journal of Organic Chemistry
Volume2015
Issue number32
DOIs
Publication statusPublished - 1 Nov 2015
Externally publishedYes

Keywords

  • Chiral pool
  • Cross-coupling
  • Homogeneous catalysis
  • Lactones
  • Levoglucosenone

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