Ligand-Enabled δ-C(sp3 )-H Borylation of Aliphatic Amines

Hediyala B Chandrashekar; Pravas Dolui; Bijin Li; Astam Mandal; Hao Liu; Srimanta Guin; Haibo Ge; Debabrata Maiti

doi:10.1002/anie.202105204

Ligand-Enabled δ-C(sp³ )-H Borylation of Aliphatic Amines

Angew Chem Int Ed Engl. 2021 Aug 9;60(33):18194-18200. doi: 10.1002/anie.202105204. Epub 2021 Jul 8.

Authors

Hediyala B Chandrashekar¹, Pravas Dolui¹, Bijin Li^{2

3}, Astam Mandal¹, Hao Liu², Srimanta Guin¹, Haibo Ge², Debabrata Maiti¹

Affiliations

¹ Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India.
² Department of Chemistry and Biochemistry, Lubbock, TX, 79409-1061, USA.
³ Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, P. R. China.

PMID: 34117691
DOI: 10.1002/anie.202105204

Abstract

Directed C-H functionalization has been realized as a complimentary technique to achieve borylation at a distal position of aliphatic amines. Here, we demonstrated the oxidative borylation at the distal δ-position of aliphatic amines using various borylating agents, a palladium catalyst, and a rightly tuned ligand in the presence of a cheap oxidant. Moreover, an organopalladium δ-C(sp³ )-H-activated intermediate has been isolated and crystallographically characterized to get mechanistic insight.

Keywords: C−H activation; Pd catalysis; mechanistic studies; δ-borylation.

Publication types

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