Axially Chiral ( R )-BINOL-, ( R )-BINAM-, and ( R )-NOBIN-Stabilized Palladium Nanoparticles for Highly Enantioselective Asymmetric Suzuki-Miyaura Cross-Coupling Reactions
- 1Mersin University , , ,
Abstract
Chiral palladium nanoparticles (PdNPs) stabilized by axially chiral 1,1′-bi-2-naphthol ((R)-BINOL), (R)-[1,1′-binaphthalene]-2,2′-diamine ((R)-BINAM), and (R)-2-amino-1,1′-binaphthalen-2-ol ((R)-NOBIN) ligands were synthesized and evaluated as heterogeneous catalysts for asymmetric Suzuki-Miyaura cross-coupling reactions. Structural and spectroscopic analyses confirmed the formation of crystalline PdNPs with narrow size distributions (2.4–2.7 nm) and ligand-induced surface chirality. Under the optimized conditions, the catalysts consistently provided high enantioselectivities, reaching ≥99% ee over a broad substrate scope comprising diverse aryl halides and boronic acids. Enantioinduction originates from the chiral environment at the nanoparticle surface, whereas catalytic efficiency is primarily determined by the steric and electronic properties of the substrate and the identity of the leaving group. (R)-BINAM-stabilized PdNPs provided superior conversions, which can be attributed to the two amine (−NH2) groups in (R)-BINAM that enable stronger metal–ligand interactions at the Pd surface. Poisoning, hot filtration, and recycling experiments support predominantly heterogeneous catalysis and demonstrate retention of activity and enantioselectivity over multiple cycles. These findings establish chiral PdNPs as efficient, reusable, and highly enantioselective catalysts for the synthesis of axially chiral biaryls.
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BibTeX
@article{gunduz2026axially,
title = {{Axially Chiral ( R )-BINOL-, ( R )-BINAM-, and ( R )-NOBIN-Stabilized Palladium Nanoparticles for Highly Enantioselective Asymmetric Suzuki-Miyaura Cross-Coupling Reactions}},
author = {Özlem Gündüz and Simay İ̇nce and Mustafa Kemal Yılmaz},
journal = {ACS Omega},
year = {2026},
month = nov,
doi = {10.1021/acsomega.6c07675},
url = {https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c07675/5464866/Axially-Chiral-R-BINOL-R-BINAM-and-R-NOBIN},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Axially Chiral ( R )-BINOL-, ( R )-BINAM-, and ( R )-NOBIN-Stabilized Palladium Nanoparticles for Highly Enantioselective Asymmetric Suzuki-Miyaura Cross-Coupling Reactions
AU - Özlem Gündüz
AU - Simay İ̇nce
AU - Mustafa Kemal Yılmaz
PY - 2026
DA - 2026/11/05
JO - ACS Omega
DO - 10.1021/acsomega.6c07675
UR - https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c07675/5464866/Axially-Chiral-R-BINOL-R-BINAM-and-R-NOBIN
AB - Chiral palladium nanoparticles (PdNPs) stabilized by axially chiral 1,1′-bi-2-naphthol ((R)-BINOL), (R)-[1,1′-binaphthalene]-2,2′-diamine ((R)-BINAM), and (R)-2-amino-1,1′-binaphthalen-2-ol ((R)-NOBIN) ligands were synthesized and evaluated as heterogeneous catalysts for asymmetric Suzuki-Miyaura cross-coupling reactions. Structural and spectroscopic analyses confirmed the formation of crystalline PdNPs with narrow size distributions (2.4–2.7 nm) and ligand-induced surface chirality. Under the optimized conditions, the catalysts consistently provided high enantioselectivities, reaching ≥99% ee over a broad substrate scope comprising diverse aryl halides and boronic acids. Enantioinduction originates from the chiral environment at the nanoparticle surface, whereas catalytic efficiency is primarily determined by the steric and electronic properties of the substrate and the identity of the leaving group. (R)-BINAM-stabilized PdNPs provided superior conversions, which can be attributed to the two amine (−NH2) groups in (R)-BINAM that enable stronger metal–ligand interactions at the Pd surface. Poisoning, hot filtration, and recycling experiments support predominantly heterogeneous catalysis and demonstrate retention of activity and enantioselectivity over multiple cycles. These findings establish chiral PdNPs as efficient, reusable, and highly enantioselective catalysts for the synthesis of axially chiral biaryls.
SN - 2470-1343
ER -