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Pd(0)-Catalyzed Directed syn-1,2-Carboboration and -Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol via a Chiral Auxiliary

preprint
revised on 22.07.2019, 16:01 and posted on 22.07.2019, 16:24 by Zhen Liu, Jiahao Chen, Xiaohan Li, Yang Gao, John Coombs, Matthew Goldfogel, Keary Engle
We report the development of palladium(0)-catalyzed syn-selective 1,2-carboboration and -silylation reactions of alkenes containing cleavable directing groups. With B2pin2or PhMe2Si–Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono-, di-, tri- and tetrasubstituted alkenes are compatible in these transformations. We further describe directed a dearomative 1,2-carboboration of electron-rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck-type alkene 1,2-difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio- and stereocontrol.

Funding

NIH-5R35GM125052-02

Bristol-Myers Squibb Unrestricted Grant

Bristol-Myers Squibb Graduate Fellowship

Nankai University College of Chemistry International Research Scholarship

Alfred P. Sloan Fellowship

Camille-Dreyfus Teacher Scholar Award

History

Email Address of Submitting Author

keary@scripps.edu

Institution

The Scripps Research Institute

Country

USA

ORCID For Submitting Author

0000-0003-2767-6556

Declaration of Conflict of Interest

No conflict of interest to declare.

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