Ruthenium-Catalyzed Hydrodefluorination with Silane as the Directing and Reducing Group

Huaquan Fang; Qiaoxing He; Guixia Liu; Zheng Huang

doi:10.1021/acs.orglett.0c03530

Ruthenium-Catalyzed Hydrodefluorination with Silane as the Directing and Reducing Group

Org Lett. 2020 Dec 4;22(23):9298-9302. doi: 10.1021/acs.orglett.0c03530. Epub 2020 Nov 23.

Authors

Huaquan Fang¹, Qiaoxing He^{1

2}, Guixia Liu^{1

3}, Zheng Huang^{1

2

4}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
² School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
³ Chang-Kung Chuang Institute, East China Normal University, Shanghai 200062, China.
⁴ School of Chemistry and Material Sciences, Hangzhou Institute of Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, China.

PMID: 33226823
DOI: 10.1021/acs.orglett.0c03530

Abstract

We describe herein an efficient and selective Ru-catalyzed intramolecular HDF directed by a silyl group, which is readily installed, and removable and transformable following the HDF reaction. The hydrosilyl group in polyfluoroaryl silane acts not only as the directing group but also as the internal reductant, enabling precise control of the ortho-selectivity and avoiding overdefluorination. Mechanistic studies reveal a plausible catalytic cycle involving a Ru(IV)-aryne intermediate.