π-Interaction-Guided Tuning of Ferrocene Redox Mediators for Shono-Type Allylation of N-Aryl Amines
4 affiliations
- 1Department of Chemistry
- 2Boston University
- 3Department of Chemistry and Biochemistry
- 4University of California
Abstract
The development of Shono-type oxidation reactions for late-stage functionalization has recently focused on the expansion of compatible nucleophiles; however, a central limitation is N-aryl, or aniline-derived, substrates due to oxidative sensitivity that leads to decomposition under direct electrolysis. Redox mediators have recently been employed to drive Shono-type oxidation reactions at lower overpotentials but are underdeveloped with aniline-type substrates. We demonstrate that electron-transfer (ET)-based ferrocene (Fc) mediators are capable of driving a rare Shono-type allylation reaction using simple allyl trifluoroborate salt with a variety of N-aryl substrates. Computational data probing the nature of ET from substrate to Fc+ suggests a distinct π-interaction, leading to our evaluation of phenyl-appended Fc (FcPh) for enhanced reactivity. We find that FcPh improves reaction efficiency across structurally diverse N-aryl substrates under controlled potential electrolysis (CPE) at applied potentials differing only by 20 mV, illustrating a distinct handle for tuning Fc redox mediators via proposed non-covalent interactions. DFT supports a working model for “out-ofcage” and “in-cage” single electron transfer (SET)pathways that provides a rationale for observed trends. In the presence of benzene co-solvent, the advantage of FcPh is suppressed, supporting the proposed role of π-interactions between FcPh and N-aryl substrates. These results highlight mediatorbased π-interactions as a strategy for tuning mediation efficiency without substantial alteration of mediator redox potential.
Related
- HTE-Guided Development of an Asymmetric Copper-Catalyzed Retro-Allylation for Stereoselective Methallylation †
- Density functional theory investigation of oxygen-deficient SnO2-x: Optoelectronic property tuning and hydrogen gas interaction
- Data-Efficient Machine Learning Potentials for Organic Reactions through Active-Learning-Guided Fine-Tuning
- Keck asymmetric allylation in natural product synthesis: applications and developments (2018–2026)
- Copper‐Catalyzed Regioconvergent and Stereodivergent Allylation and Alkenylation of Styrenes via Bromo‐Acyloxy Transposition
BibTeX
@misc{guo2026πinteractionguided,
title = {{π-Interaction-Guided Tuning of Ferrocene Redox Mediators for Shono-Type Allylation of N-Aryl Amines}},
author = {Yahui Guo and Siyuan Su and Lupita S. Ramirez and XiaoAn Wu and Osvaldo Gutierrez and Joseph Derosa},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008696/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008696/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - π-Interaction-Guided Tuning of Ferrocene Redox Mediators for Shono-Type Allylation of N-Aryl Amines
AU - Yahui Guo
AU - Siyuan Su
AU - Lupita S. Ramirez
AU - XiaoAn Wu
AU - Osvaldo Gutierrez
AU - Joseph Derosa
PY - 2026
DA - 2026/09/11
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008696/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008696/v1
AB - The development of Shono-type oxidation reactions for late-stage functionalization has recently focused on the expansion of compatible nucleophiles; however, a central limitation is N-aryl, or aniline-derived, substrates due to oxidative sensitivity that leads to decomposition under direct electrolysis. Redox mediators have recently been employed to drive Shono-type oxidation reactions at lower overpotentials but are underdeveloped with aniline-type substrates. We demonstrate that electron-transfer (ET)-based ferrocene (Fc) mediators are capable of driving a rare Shono-type allylation reaction using simple allyl trifluoroborate salt with a variety of N-aryl substrates. Computational data probing the nature of ET from substrate to Fc+ suggests a distinct π-interaction, leading to our evaluation of phenyl-appended Fc (FcPh) for enhanced reactivity. We find that FcPh improves reaction efficiency across structurally diverse N-aryl substrates under controlled potential electrolysis (CPE) at applied potentials differing only by 20 mV, illustrating a distinct handle for tuning Fc redox mediators via proposed non-covalent interactions. DFT supports a working model for “out-ofcage” and “in-cage” single electron transfer (SET)pathways that provides a rationale for observed trends. In the presence of benzene co-solvent, the advantage of FcPh is suppressed, supporting the proposed role of π-interactions between FcPh and N-aryl substrates. These results highlight mediatorbased π-interactions as a strategy for tuning mediation efficiency without substantial alteration of mediator redox potential.
ER -