95752-87-7Relevant articles and documents
Ni-Catalyzed Borylation of Aryl Sulfoxides
Huang, Mingming,Wu, Zhu,Krebs, Johannes,Friedrich, Alexandra,Luo, Xiaoling,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
, p. 8149 - 8158 (2021/05/10)
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-C6H4){(SO)-4-MeO-C6H4}] 4. For complex 5, the isomer trans-[Ni(ICy)2(C6H5)(OSC6H5)] 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(C6H5)(OSC6H5)] 5-I is in equilibrium with the S-bonded isomer trans-[Ni(ICy)2(C6H5)(SOC6H5)] 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(C6H5)(η2-{SO}-C6H5)], which lies only 10.8 kcal/mol above 5.
Ni-Catalyzed Borylation of Aryl Fluorides via C-F Cleavage
Liu, Xiang-Wei,Echavarren, Javier,Zarate, Cayetana,Martin, Ruben
supporting information, p. 12470 - 12473 (2015/10/19)
A Ni-catalyzed borylation via C-F activation is described. This protocol is distinguished by a wide scope, including unactivated fluoroarenes, without compromising its efficiency and scalability, thus representing a significant step-forward toward the implementation of C-F activation protocols.
Borylation of organo halides and triflates using tetrakis(dimethylamino) diboron
Bello, Charles S.,Schmidt-Leithoff, Joachim
, p. 6230 - 6235,6 (2012/12/11)
We report a new in situ borylation method using tetrakis(dimethylamino) diboron, DMA4B2, in the presence of a diol. Our method uses standard borylation conditions and readily available Pd-catalysts. The scope of this method includes aryl halides and triflates as well as vinyl halides and triflates. The method successfully works with a broad range of diols, enabling the selection of the best boronic ester for subsequent Suzuki coupling.