β-Selective C(sp³)-H functionalization of alkyl boronates using photoredox catalysis.
- 1Department of Chemistry, Indiana University, Bloomington, IN USA.
Abstract
Alkyl boronates are a versatile class of organic molecules that have transformed chemical synthesis and had a broad impact in drug discovery, agrochemistry and materials research. For over 50 years, the conventional use of alkyl boronates has been the direct reaction of the C-B bond for the formation of C-C, C-N, C-O and C-X bonds. Here we report the use of alkyl boronates as directing groups to perform site-selective C(sp3)-H functionalization at the distal site. This methodology involves classic Lewis pair chemistry; it uses an alkyl-BF2, generated in situ from alkyl trifluoroborate salts, as a Lewis acid and 2-haloheteroarene as a Lewis base. Under mild photoredox reaction conditions, we are able to site-selectively functionalize the β-position of a wide range of alkyl trifluoroborate salts with the corresponding heteroarene through a cascade sequence of single-electron reduction, hydrogen atom transfer and intramolecular heteroaryl migration. This transformation effectively upgrades alkyl boron compounds into structurally complex heteroarene-containing building blocks.
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BibTeX
@article{hazra2026βselective,
title = {{β-Selective C(sp³)-H functionalization of alkyl boronates using photoredox catalysis.}},
author = {Partha Sarathi Hazra and Makaya Robinson and M Kevin Brown},
journal = {Nature synthesis},
year = {2026},
month = jul,
doi = {10.1038/s44160-026-01106-4},
url = {https://europepmc.org/article/MED/42996630},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - β-Selective C(sp³)-H functionalization of alkyl boronates using photoredox catalysis.
AU - Partha Sarathi Hazra
AU - Makaya Robinson
AU - M Kevin Brown
PY - 2026
DA - 2026/07/10
JO - Nature synthesis
DO - 10.1038/s44160-026-01106-4
UR - https://europepmc.org/article/MED/42996630
AB - Alkyl boronates are a versatile class of organic molecules that have transformed chemical synthesis and had a broad impact in drug discovery, agrochemistry and materials research. For over 50 years, the conventional use of alkyl boronates has been the direct reaction of the C-B bond for the formation of C-C, C-N, C-O and C-X bonds. Here we report the use of alkyl boronates as directing groups to perform site-selective C(sp3)-H functionalization at the distal site. This methodology involves classic Lewis pair chemistry; it uses an alkyl-BF2, generated in situ from alkyl trifluoroborate salts, as a Lewis acid and 2-haloheteroarene as a Lewis base. Under mild photoredox reaction conditions, we are able to site-selectively functionalize the β-position of a wide range of alkyl trifluoroborate salts with the corresponding heteroarene through a cascade sequence of single-electron reduction, hydrogen atom transfer and intramolecular heteroaryl migration. This transformation effectively upgrades alkyl boron compounds into structurally complex heteroarene-containing building blocks.
SN - 2731-0582
ER -