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. 2024 Oct 4;89(19):14571-14576.
doi: 10.1021/acs.joc.4c01701. Epub 2024 Sep 25.

Iron-Catalyzed Transfer Hydrogenation of Allylic Alcohols with Isopropanol

Md Abdul Bari  1 , Salma A Elsherbeni  1   2 , Tahir Maqbool  1   3 , Daniel E Latham  1 , Edward B Gushlow  1 , Emily J Harper  1 , Louis C Morrill  1   4
Affiliations

Iron-Catalyzed Transfer Hydrogenation of Allylic Alcohols with Isopropanol

Md Abdul Bari et al. J Org Chem. .

Abstract

Herein, we report an iron-catalyzed transfer hydrogenation of allylic alcohols. The operationally simple protocol employs a well-defined bench stable (cyclopentadienone)iron(0) carbonyl complex as a precatalyst in combination with K2CO3 (4 mol %) and isopropanol as the hydrogen donor. A diverse range of allylic alcohols undergo transfer hydrogenation to form the corresponding alcohols in good yields (33 examples, ≤83% isolated yield). The scope and limitations of the method have been investigated, and experiments that shed light on the reaction mechanism have been conducted.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Background and Context
Scheme 2
Scheme 2. Scope of Iron-Catalyzed Transfer Hydrogenation of Allylic Alcohols
With 5.5 mmol of allylic alcohol as the starting material. As determined by 1H NMR analysis of the crude reaction mixture with 1,3,5-trimethylbenzene as the internal standard. For 48 h. Reactions performed using 1 mmol of allylic alcohol starting material and reagent grade i-PrOH. Isolated yields after chromatographic purification unless stated otherwise. RSM = recovered starting material.
Scheme 3
Scheme 3. Mechanistic Experiments
Yields and deuterium incorporation determined by 1H NMR analysis of the crude reaction mixture with 1,3,5-trimethylbenzene as the internal standard.
Scheme 4
Scheme 4. Plausible Mechanism
See this image and copyright information in PMC

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