Indole Nucleophile Triggers Mechanistic Divergence in Ni-Photoredox N–Arylation DOI Creative Commons

Kevin Liang,

Olivia Taylor,

Angie L. López

et al.

Published: June 25, 2024

This study presents a Ni-photoredox method for indole N-arylation, broadening the range of substrates to include indoles with unprotected C3-positions and base-sensitive groups. Through detailed mechanistic inquiries, Ni(I/III) mechanism was uncovered, distinct from those commonly proposed Ni-catalyzed amine, thiol, alcohol arylation, as well Ni(0/II/III) cycle identified amide arylation under almost identical conditions. The key finding is formation Ni(I) intermediate bearing nucleophile ligand prior oxidative addition, which rare carbon-heteroatom coupling has profound impact on reaction kinetics scope. pre-coordination renders more electron-rich intermediate, broadens scope by enabling fast reactivity even challenging aryl bromide substrates. Thus, this work highlights often-overlooked influence X-type ligands Ni addition rates illustrates yet another divergence in C–heteroatom couplings.

Language: Английский

Indole Nucleophile Triggers Mechanistic Divergence in Ni-Photoredox N–Arylation DOI Creative Commons

Kevin Liang,

Olivia Taylor,

Angie L. López

et al.

Published: June 25, 2024

This study presents a Ni-photoredox method for indole N-arylation, broadening the range of substrates to include indoles with unprotected C3-positions and base-sensitive groups. Through detailed mechanistic inquiries, Ni(I/III) mechanism was uncovered, distinct from those commonly proposed Ni-catalyzed amine, thiol, alcohol arylation, as well Ni(0/II/III) cycle identified amide arylation under almost identical conditions. The key finding is formation Ni(I) intermediate bearing nucleophile ligand prior oxidative addition, which rare carbon-heteroatom coupling has profound impact on reaction kinetics scope. pre-coordination renders more electron-rich intermediate, broadens scope by enabling fast reactivity even challenging aryl bromide substrates. Thus, this work highlights often-overlooked influence X-type ligands Ni addition rates illustrates yet another divergence in C–heteroatom couplings.

Language: Английский

Citations

1