Iron-catalyzed alkyne alkylzincation affected by counterions

Lu-Jie Li, Qiao Zhang, Peng He, Ming-Yao Huang and Shou-Fei Zhu ()
Additional contact information
Lu-Jie Li: Nankai University
Qiao Zhang: Nankai University
Peng He: Nankai University
Ming-Yao Huang: Nankai University
Shou-Fei Zhu: Nankai University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: Abstract Metal complex catalysts typically comprise three components: ligands, central metals, and counterions. The counterion profoundly influences the activity and selectivity of numerous catalytic reactions, while such a phenomenon is rarely observed in carbozincation reactions. Herein, we discover that the catalytic efficiency of iron-catalyzed alkylzincation of alkynes is markedly enhanced when the weakly coordinating bulky counterion tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ([BArF4]−) is incorporated into the reaction. This approach yields ionic iron catalysts with exceptional activity (up to 32,900 TON), regioselectivity (mostly >95:5), and stereoselectivity (mostly >95:5) in both alkylzincation reactions of terminal and internal alkynes. Notably, the methylzincation of non-activated terminal and internal alkynes is rendered feasible. This methodology also enables the efficient synthesis of a diverse array of biologically active molecules and their key intermediates. Mechanistic investigations suggest that a cationic Fe(II) species serves as the active catalytic species and the weakly coordinating bulky counterion stabilizes a cationic iron(II) alkyl complex without competing with the alkyne substrate.

Date: 2025
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-025-62460-z Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-62460-z

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-025-62460-z

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().