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Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
Published on: November 30, 2022
An Olefinic 1,2-Boryl-Migration Enabled by Radical Addition: Construction of gem-Bis(boryl)alkanes
Binlin Zhao1, Zexian Li1, Yixiao Wu2
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Abstract:
A series of in situ formed alkenyl diboronate complexes from alkenyl Grignard reagents (commercially available or prepared from alkenyl bromides and Mg) with B2 Pin2 (bis(pinacolato)diboron) react with diverse alkyl halides by a Ru photocatalyst to give various gem-bis(boryl)alkanes. Alkyl radicals add efficiently to the alkenyl diboronate complexes, and the adduct radical anions undergo radical-polar crossover, specifically, a 1,2-boryl-anion shift from boron to the α-carbon sp2 center. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage functionalization in complex compounds. Measurements of the quantum yield reveal that a radical-chain mechanism is operative in which the alkenyl diboronates acts as reductive quencher for the excited state of the photocatalyst.
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