4.8 Article

Dual Nickel/Photoredox-Catalyzed Site-Selective Cross-Coupling of 1,2-Bis-Boronic Esters Enabled by 1,2-Boron Shifts

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 34, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202207988

Keywords

Boronic Esters; Cross-Coupling; Dual Catalysis; Nickel; Photoredox Catalysis

Funding

  1. DFG [442129649]
  2. China Scholarship Council

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This study reports a nickel/photoredox-catalyzed site-selective mono-deboronative arylation of 1,2-bis-boronic esters, which allows for selective coupling of the more sterically hindered secondary/tertiary positions. This is achieved by utilizing a 1,2-boron shift of primary β-boryl radicals to the thermodynamically favored secondary/tertiary radicals for arylation. The mild conditions of this method are suitable for a wide range of aryl halides, resulting in good yields and high regioselectivity. Additionally, this method allows for stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to give trans-substituted products.
Site-selective transition-metal-catalyzed mono-deboronative cross-couplings of 1,2-bis-boronic esters are valuable methods for the synthesis of functionalized organoboron compounds. However, such cross-couplings are limited to reaction of the sterically less hindered primary boronic ester. Herein, we report a nickel/photoredox-catalyzed mono-deboronative arylation of 1,2-bis-boronic esters that is selective for coupling of the more sterically hindered secondary/tertiary position. This is achieved by taking advantage of a 1,2-boron shift of primary beta-boryl radicals to the thermodynamically favored secondary/tertiary radicals, which are subsequently intercepted by the nickel catalyst to enable arylation. The mild conditions are amenable to a broad range of aryl halides to give beta-aryl boronic ester products in good yields and with high regioselectivity. This method also allows stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to give trans-substituted products.

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