Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study

Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study
Jianyou Mao, Patrick J. Walsh, Samuel P. McCollom, R. Thomas Williamson, Ana Bellomo, Brian C. Manor, Christopher J. Welch, Sonia Montel, Tiezheng Jia, Erik L. Regalado, Neil C. Tomson, Mengnan Zhang, Spencer D. Dreher
A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated. Many of the sulfoxides prepared herein would be difficult to prepare via classic enantioselective oxidation of sulfides, including Ph(Ph-d5)SO (90% ee, 95% yield). A DFT-based computational study suggested that chiral induction originates from two primary factors: (i) both a kinetic and a thermodynamic preference for oxidative addition that places the bromide trans to the JosiPhos-diarylphosphine moiety and (ii) Curtin–Hammett-type control over the interconversion between O- and S-bound isomers of palladium sulfenate species following rapid interconversion between re- and si-bound transmetalation products, re/si-Pd–OSPh (re/si-PdO-trans).

Publisher URL: http://dx.doi.org/10.1021/jacs.7b03623

DOI: 10.1021/jacs.7b03623

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