Axial shielding of Pd(II) complexes enables perfect stereoretention in Suzuki-Miyaura cross-coupling of Csp3 boronic acids

Jonathan W. Lehmann, Ian T. Crouch, Daniel J. Blair, Melanie Trobe, Pulin Wang, Junqi Li and Martin D. Burke ()
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Jonathan W. Lehmann: University of Illinois at Urbana-Champaign
Ian T. Crouch: University of Illinois at Urbana-Champaign
Daniel J. Blair: University of Illinois at Urbana-Champaign
Melanie Trobe: University of Illinois at Urbana-Champaign
Pulin Wang: University of Illinois at Urbana-Champaign
Junqi Li: University of Illinois at Urbana-Champaign
Martin D. Burke: University of Illinois at Urbana-Champaign

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: Abstract Stereocontrolled Csp3 cross-coupling can fundamentally change the types of chemical structures that can be mined for molecular functions. Although considerable progress in achieving the targeted chemical reactivity has been made, controlling stereochemistry in Csp3 cross-coupling remains challenging. Here we report that ligand-based axial shielding of Pd(II) complexes enables Suzuki-Miyaura cross-coupling of unactivated Csp3 boronic acids with perfect stereoretention. This approach leverages key differences in spatial orientation between competing pathways for stereoretentive and stereoinvertive transmetalation of Csp3 boronic acids to Pd(II). We show that axial shielding enables perfectly stereoretentive cross-coupling with a range of unactivated secondary Csp3 boronic acids, as well as the stereocontrolled synthesis of xylarinic acid B and all of its Csp3 stereoisomers. We expect these ligand design principles will broadly enable the continued search for practical and effective methods for stereospecific Csp3 cross-coupling.

Date: 2019
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DOI: 10.1038/s41467-019-09249-z

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