Nickel-catalyzed trifluoromethylthiolation of Csp2–O bonds† †Electronic supplementary information (ESI) available: Experimental procedures, spectroscopic data, ReactIR studies, computational information and Cartesian coordinates of calculated species as well as full ref. 17 are given. See DOI: 10.1039/c5sc03359d Click here for additional data file.
نویسندگان
چکیده
While nickel catalysts have previously been shown to activate even the least reactive Csp–O bonds, i.e. aryl ethers, in the context of C–C bond formation, little is known about the reactivity limits and molecular requirements for the introduction of valuable functional groups under homogeneous nickel catalysis. We identified that due to the high reactivity of Ni-catalysts, they are also prone to react with existing or installed functional groups, which ultimately causes catalyst deactivation. The scope of the Ni-catalyzed coupling protocol will therefore be dictated by the reactivity of the functional groups towards the catalyst. Herein, we showed that the application of computational tools allowed the identification of matching functional groups in terms of suitable leaving groups and tolerated functional groups. This allowed for the development of the first efficient protocol to trifluoromethylthiolate Csp–O bonds, giving the mild and operationally simple C–SCF3 coupling of a range of aryl, vinyl triflates and nonaflates. The novel methodology was also applied to biologically active and pharmaceutical relevant targets, showcasing its robustness and wide applicability.
منابع مشابه
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Fachbereich Chemie, TU Kaiserslautern, Kaiserslautern, Germany. E-mail: goossen@ Department of Chemical Sciences, Indian In (IISER) Kolkata, Mohanpur 741246, India. E † Electronic supplementary information dispersion corrected density functional NPA charges and frontier molecular Cartesian coordinates and absolute ene and transition states. Complete referen 10.1039/c4sc03906h Cite this: Chem. S...
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Department of Organic Chemistry II, Unive P.O. Box 644, 48080 Bilbao, Spain Departamento de Śıntesis y Estructura de Bi y Catálisis Homogénea (ISQCH), Universida Servicio de Resonancia Magnética Nuclear, C (CEQMA), Universidad de Zaragoza, CSIC, † Electronic supplementary information procedures and characterization of all NMR spectra and HPLC chromatogram Cartesian coordinates of all stationary...
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Department of Chemistry, Beijing Normal U [email protected]; [email protected]; Fax: Institut für Anorganische und Analyti Braunschweig, Hagenring 30, 38106 Brau tu-bs.de; Fax: +49-531-3915387; Tel: +49-53 † Electronic supplementary information ( all stationary points optimized at B3PW9 For ESI and crystallographic data in CI 10.1039/c5sc01684c ‡ These authors contributed equally to th Cite this: ...
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