5097-05-2Relevant 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.
supporting information, 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.
Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
supporting information, (2019/06/13)
Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
Palladium-Catalyzed Enantioselective C?H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization
Zhu, Yu-Chao,Li, Yan,Zhang, Bo-Chao,Zhang, Feng-Xu,Yang, Yi-Nuo,Wang, Xi-Sheng
supporting information, p. 5129 - 5133 (2018/03/27)
The first example of PdII-catalyzed enantioselective C?H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) throu