---
OA_place: publisher
OA_type: hybrid
PlanS_conform: '1'
_id: '23094'
abstract:
- lang: eng
text: The formation of C(sp2)–heteroatom bonds through cross-coupling catalysis
is central to the synthesis of pharmaceuticals, agrochemicals and materials. Whereas
Pd0/PdII catalysis requires substrate-specific ligand optimization to balance
the competing demands of oxidative addition and reductive elimination, NiI/NiIII
catalysis offers a complementary strategy because the bond-forming step is intrinsically
favourable. However, contemporary NiI/NiIII methodologies suffer from insufficient
oxidative addition reactivity, restricting the aryl halide scope and requiring
high catalyst loadings. Here we show that mechanistically guided ligand design
overcomes these limitations. Together with a non-nucleophilic base additive that
promotes direct visible-light generation of NiI from a bench-stable NiII precatalyst,
this ligand design enables the coupling of electron-rich aryl bromides with N-,
O-, S- and P-based nucleophiles at nickel loadings as low as 100 ppm. The method
is compatible with sterically encumbered nucleophiles and enables gram-scale synthesis
and late-stage functionalization of complex molecules.
acknowledged_ssus:
- _id: LifeSc
- _id: MassSpec
- _id: NMR
- _id: M-Shop
acknowledgement: We acknowledge ISTA for generous financial support. This research
was supported by the Scientific Service Units (SSU) of ISTA through resources provided
by the Lab Support Facility, Mass Spec Facility, NMR facility and the Miba Machine
Shop. We specifically thank A. Paraskevopoulou for high-resolution mass spectrometry
measurements. B.P. acknowledges the Austrian Science Fund (PAT 1250924) and the
ACS GCI Pharmaceutical Roundtable for funding. T.B. thanks the European Union’s
Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie
Grant Agreement No. 101034413. D.B. acknowledges funding from the Czech Science
Foundation (25-17760M). Open access funding provided by Institute of Science and
Technology (IST Austria).
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Aleksander
full_name: Bena, Aleksander
id: 4197c39e-e8ec-11ed-86cb-afed934cd664
last_name: Bena
- first_name: Trisha
full_name: Banik, Trisha
id: 506b8e06-c59a-11ee-a1af-ae470719e7d3
last_name: Banik
- first_name: Christos
full_name: Giannoudis, Christos
id: 1bd506c6-e8ec-11ed-86cb-d495f63f2dcd
last_name: Giannoudis
- first_name: Florian
full_name: Ortis, Florian
id: e34c9177-3208-11ee-ac71-a6a15cf2ef29
last_name: Ortis
orcid: 0000-0002-0458-5187
- first_name: Daniel
full_name: Bím, Daniel
last_name: Bím
- first_name: Haralds
full_name: Baunis, Haralds
id: 2eea55ec-e8ec-11ed-86cb-d9c76787acfe
last_name: Baunis
- first_name: Gayathri
full_name: Palissery, Gayathri
id: b02c9d47-50c9-11ef-b52e-b2180bf00ccd
last_name: Palissery
- first_name: Bartholomäus
full_name: Pieber, Bartholomäus
id: 93e5e5b2-0da6-11ed-8a41-af589a024726
last_name: Pieber
orcid: 0000-0001-8689-388X
citation:
ama: Bena A, Banik T, Giannoudis C, et al. Ligand design broadens NiI-catalysed
C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings. Nature
Catalysis. 2026. doi:10.1038/s41929-026-01616-6
apa: Bena, A., Banik, T., Giannoudis, C., Ortis, F., Bím, D., Baunis, H., … Pieber,
B. (2026). Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of
aryl bromides at low catalyst loadings. Nature Catalysis. Springer Nature.
https://doi.org/10.1038/s41929-026-01616-6
chicago: Bena, Aleksander, Trisha Banik, Christos Giannoudis, Florian Ortis, Daniel
Bím, Haralds Baunis, Gayathri Palissery, and Bartholomäus Pieber. “Ligand Design
Broadens NiI-Catalysed C(Sp2)–Heteroatom Couplings of Aryl Bromides at Low Catalyst
Loadings.” Nature Catalysis. Springer Nature, 2026. https://doi.org/10.1038/s41929-026-01616-6.
ieee: A. Bena et al., “Ligand design broadens NiI-catalysed C(sp2)–heteroatom
couplings of aryl bromides at low catalyst loadings,” Nature Catalysis.
Springer Nature, 2026.
ista: Bena A, Banik T, Giannoudis C, Ortis F, Bím D, Baunis H, Palissery G, Pieber
B. 2026. Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl
bromides at low catalyst loadings. Nature Catalysis.
mla: Bena, Aleksander, et al. “Ligand Design Broadens NiI-Catalysed C(Sp2)–Heteroatom
Couplings of Aryl Bromides at Low Catalyst Loadings.” Nature Catalysis,
Springer Nature, 2026, doi:10.1038/s41929-026-01616-6.
short: A. Bena, T. Banik, C. Giannoudis, F. Ortis, D. Bím, H. Baunis, G. Palissery,
B. Pieber, Nature Catalysis (2026).
corr_author: '1'
das_tickbox: '1'
dataavailabilitystatement: All data are available from the authors upon request.
date_created: 2026-10-11T22:02:06Z
date_published: 2026-09-29T00:00:00Z
date_updated: 2026-10-14T06:32:42Z
day: '29'
department:
- _id: BaPi
- _id: GradSch
- _id: RaKl
doi: 10.1038/s41929-026-01616-6
ec_funded: 1
fulldoi: https://doi.org/10.1038/s41929-026-01616-6
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1038/s41929-026-01616-6
month: '09'
oa: 1
oa_version: Published Version
project:
- _id: 8f1d607d-16d5-11f0-9cad-ab453295ba5e
grant_number: PAT 1250924
name: Photoactive ligands for transformative nickel catalysis
- _id: fc2ed2f7-9c52-11eb-aca3-c01059dda49c
call_identifier: H2020
grant_number: '101034413'
name: 'IST-BRIDGE: International postdoctoral program'
publication: Nature Catalysis
publication_identifier:
eissn:
- 2520-1158
publication_status: epub_ahead
publisher: Springer Nature
quality_controlled: '1'
researchdata_availability: upon request
scopus_import: '1'
status: public
supplementarymaterial: yes
title: Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides
at low catalyst loadings
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2026'
...