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. 2025 Sep 26;16(1):8379.
doi: 10.1038/s41467-025-63515-x.

Fe-electrocatalytic deoxygenative Giese reaction

Longhui Yu #  1 , Shangzhao Li #  1 , Hiroshige Ogawa #  1 , Yilin Ma  1 , Qing Chen  1 , Ken Yamazaki  2 , Yuuya Nagata  3   4 , Hugh Nakamura  5
Affiliations

Fe-electrocatalytic deoxygenative Giese reaction

Longhui Yu et al. Nat Commun. .

Abstract

A redox-neutral Fe-electrocatalytic deoxygenative Giese reaction is reported. Hydroxyl groups are among the most abundant functional groups, and thus, the development of efficient reactions for their conversion has significant importance in medicinal and process chemistry. Here, we present a redox-neutral Giese reaction via anodic oxidation to generate phosphonium ions in combination with a cathodic reduction to yield low-valent Fe-catalysts. This reaction represents a promising example of a redox-neutral reaction using an Fe-catalyst and electrochemistry. The results obtained in this study will facilitate the exploration of a wide range of novel reactions employing this redox cycle in the future.

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Conflict of interest statement

Competing interests: The authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Evolution of deoxygenative C-C bond formation from traditional approaches to redox-neutral Fe-electrocatalytic deoxygenative Giese reaction: context, concept, and optimization.
A Overview of existing strategies for deoxygenative C–C bond formation from alcohol. B Concept of the Fe-electrocatalytic deoxygenative Giese reaction. C Optimization of the reaction conditions.
Fig. 2
Fig. 2. Substrate scope of Fe-electrocatalyzed deoxygenative Giese reaction: reactivity across styrene and acrylate derivatives.
A Scope of styrene derivatives. B Scope of acrylate derivatives. aIsolated yields. bFeCl2 (15 mol%), IPr·HCl (15 mol%), PPh3 (4 eq.), TBAB (4 eq.), and DIPEA (4 eq.) were used. cTBAI (4 eq.) was used instead of TBAB. dFeCl2 (20 mol%), IPr·HCl (20 mol%), PPh3 (6 eq.), TBAB (4 eq.), and DIPEA (2 eq.) were used.
Fig. 3
Fig. 3. Substrate scope of Fe-electrocatalyzed deoxygenative Giese reaction: reactivity across 1° alcohols and 2° alchohols.a,b.
A Scope of 1° alcohols. B Scope of 2° alcohols. aIsolated yields. bFeCl2 (15 mol%), IPr·HCl (15 mol%), PPh3 (4 eq.), TBAB (4 eq.), and DIPEA (4 eq.) were used for 40. FeCl2 (20 mol%), IPr·HCl (20 mol%), PPh3 (6 eq.), TBAB (4 eq.), and DIPEA (2 eq.) were used for 41.
Fig. 4
Fig. 4. Mechanistic studies and application to the gram-scale diversification.
A Mechanistic studies. B Control experiments. C Proposed reaction mechanism. D Application to gram-scale synthesis and diversification.
Fig. 5
Fig. 5. Energy profile for the Fe-catalyzed halogen atom transfer.
Schematic representation of XAT transition state, computed at the SMD(DMA)-(U)B3LYP-D3BJ/BS1 level of theory. Energies (kcal mol–1) and bond lengths (Å) are provided in the insert.
Fig. 6
Fig. 6. Further mechanistic studies and 1H NMR reaction monitoring.
A Cyclic voltammetry. B limitation of the substrates. C NMR trace.
See this image and copyright information in PMC

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