A Versatile Bis-Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

Belinda E. Hetzler, Giulio Volpin, Elisa Vignoni, Ana G. Petrovic, Gloria Proni, Chunhua T. Hu, Dirk Trauner

Research output: Contribution to journalArticle

Abstract

Allylboron reagents are popular in synthesis owing to their versatility and the predictable stereochemical outcomes of their reactions with carbonyl compounds. Herein, we describe the synthesis of (Z,Z)-hexadienyl bis-boronate 1, a configurationally stable, crystalline, and easy to handle compound, which represents a class of bis-allylic boron reagents with heretofore untapped synthetic potential. In combination with a chiral phosphoric acid catalyst, the reagent can be employed for the enantioselective allyl transfer reaction to a variety of one-pot transformations, enabling swift access to functionalized 1,n-diols. The in situ conversion of the reagent into the corresponding bis-borinic ester allows for the direct and diastereoselective two-fold allyl transfer to aldehydes. This affords C2- or Ci-symmetric stereotetrads containing a 1,4-diol moiety for natural product synthesis. The usefulness of our method was demonstrated with a short synthesis of the lignan (±)-neo-olivil.

Original languageEnglish (US)
Pages (from-to)14276-14280
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number43
DOIs
StatePublished - Oct 22 2018

Fingerprint

Carbonyl compounds
Lignans
Boron
Phosphoric acid
Biological Products
Aldehydes
Esters
Crystalline materials
Catalysts
phosphoric acid
olivil

Keywords

  • allyboron
  • chiral phosphoric acid
  • natural products
  • stereospecific reactions
  • synthetic methods

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Hetzler, B. E., Volpin, G., Vignoni, E., Petrovic, A. G., Proni, G., Hu, C. T., & Trauner, D. (2018). A Versatile Bis-Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols. Angewandte Chemie - International Edition, 57(43), 14276-14280. https://doi.org/10.1002/anie.201808234

A Versatile Bis-Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols. / Hetzler, Belinda E.; Volpin, Giulio; Vignoni, Elisa; Petrovic, Ana G.; Proni, Gloria; Hu, Chunhua T.; Trauner, Dirk.

In: Angewandte Chemie - International Edition, Vol. 57, No. 43, 22.10.2018, p. 14276-14280.

Research output: Contribution to journalArticle

Hetzler, BE, Volpin, G, Vignoni, E, Petrovic, AG, Proni, G, Hu, CT & Trauner, D 2018, 'A Versatile Bis-Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols', Angewandte Chemie - International Edition, vol. 57, no. 43, pp. 14276-14280. https://doi.org/10.1002/anie.201808234
Hetzler, Belinda E. ; Volpin, Giulio ; Vignoni, Elisa ; Petrovic, Ana G. ; Proni, Gloria ; Hu, Chunhua T. ; Trauner, Dirk. / A Versatile Bis-Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols. In: Angewandte Chemie - International Edition. 2018 ; Vol. 57, No. 43. pp. 14276-14280.
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