Desymmetrization of C2 -Symmetric Bis(Boronic Esters) by Zweifel Olefinations

Yannick Linne; Axel Schönwald; Sebastian Weißbach; Markus Kalesse

doi:10.1002/chem.202000599

Desymmetrization of C₂ -Symmetric Bis(Boronic Esters) by Zweifel Olefinations

Chemistry. 2020 Jun 26;26(36):7998-8002. doi: 10.1002/chem.202000599. Epub 2020 Jun 3.

Authors

Yannick Linne^{1

2}, Axel Schönwald¹, Sebastian Weißbach¹, Markus Kalesse^{1

2

3}

Affiliations

¹ Institute for Organic Chemistry, Gottfried Wilhelm Leibniz Universität Hannover, Schneiderberg 1B, 30167, Hannover, Germany.
² Centre of Biomolecular Drug Research (BMWZ), Gottfried Wilhelm Leibniz Universität Hannover, Schneiderberg 38, 30167, Hannover, Germany.
³ Helmholtz Centre for Infection Research (HZI), Inhoffenstrasse 7, 38124, Braunschweig, Germany.

Abstract

anti-Configured 1,3-dimethyl deoxypropionate motifs are important sub structures in natural products. Herein, we describe a bidirectional approach for the rapid construction of natural products featuring such motifs by using C₂ -symmetrical 1,3-bis(boronic esters). As for its application in convergent syntheses it was important to establish a selective mono-Zweifel olefination we describe the scope and limitations by using different 1,3-bis(boronic esters) and nucleophiles. This protocol takes advantage of the combination of the Hoppe-Matteson-Zweifel chemistry, which was elegantly put into practice by Aggarwal et al. In order to show its applicability the total syntheses of two natural products, serricornin and (+)-invictolide, were performed.

Keywords: C2-symmetry; desymmetrization; lithiation-borylation chemistry; mono-Zweifel olefination; natural product synthesis.