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Updated: Nov 9, 2025
Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
Published on: November 30, 2022
Ni-Catalyzed Borylation of Aryl Sulfoxides
Mingming Huang1, Zhu Wu1, Johannes Krebs1
1Institut für Anorganische Chemie and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Abstract:
A nickel/N-heterocyclic carbene (NHC) catalytic system has been developed for the borylation of aryl sulfoxides with B2 (neop)2 (neop=neopentyl glycolato). A wide range of aryl sulfoxides with different electronic and steric properties were converted into the corresponding arylboronic esters in good yields. The regioselective borylation of unsymmetric diaryl sulfoxides was also feasible leading to borylation of the sterically less encumbered aryl substituent. Competition experiments demonstrated that an electron-deficient aryl moiety reacts preferentially. The origin of the selectivity in the Ni-catalyzed borylation of electronically biased unsymmetrical diaryl sulfoxide lies in the oxidative addition step of the catalytic cycle, as oxidative addition of methoxyphenyl 4-(trifluoromethyl)phenyl sulfoxide to the Ni(0) complex occurs selectively to give the structurally characterized complex trans-[Ni(ICy)2 (4-CF3 -C6 H4 ){(SO)-4-MeO-C6 H4 }] 4. For complex 5, the isomer trans-[Ni(ICy)2 (C6 H5 )(OSC6 H5 )] 5-I was structurally characterized in which the phenyl sulfinyl ligand is bound via the oxygen atom to nickel. In solution, the complex trans-[Ni(ICy)2 (C6 H5 )(OSC6 H5 )] 5-I is in equilibrium with the S-bonded isomer trans-[Ni(ICy)2 (C6 H5 )(SOC6 H5 )] 5, as shown by NMR spectroscopy. DFT calculations reveal that these isomers are separated by a mere 0.3 kJ/mol (M06/def2-TZVP-level of theory) and connected via a transition state trans-[Ni(ICy)2 (C6 H5 )(η2 -{SO}-C6 H5 )], which lies only 10.8 kcal/mol above 5.
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