1,2-Hydroboration of Pyridines by Organomagnesium

Xinli Liu; Bingwen Li; Xiufang Hua; Dongmei Cui

doi:10.1021/acs.orglett.0c01388

1,2-Hydroboration of Pyridines by Organomagnesium

Org Lett. 2020 Jul 2;22(13):4960-4965. doi: 10.1021/acs.orglett.0c01388. Epub 2020 Jun 11.

Authors

Xinli Liu¹, Bingwen Li², Xiufang Hua^{1

3}, Dongmei Cui^{1

3}

Affiliations

¹ State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
² Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.
³ University of Chinese Academy of Sciences, Changchun Branch, Changchun 130022, China.

PMID: 32525320
DOI: 10.1021/acs.orglett.0c01388

Abstract

Hydroboration of pyridine derivatives at room temperature with earth-abundant and biocompatible magnesium catalysts ligated by phosphinimino amides is developed. Fine turnover frequency (TOF) and distinguished 1,2-regioselectivity have been achieved. The exclusive chemoselective carbonyl hydroboration happens with competitive TOF. A HBpin assisted mechanism is deduced by the reaction rate law, activation parameters, and kinetic isotope effect (KIE) in combination with DFT calculations. To our knowledge, this is the first example of pyridine 1,2-dearomatization by Mg-based catalysts.

Publication types

Research Support, Non-U.S. Gov't