Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2023 Aug 1;24(15):12299.
doi: 10.3390/ijms241512299.

Systematic Development of Vanadium Catalysts for Sustainable Epoxidation of Small Alkenes and Allylic Alcohols

José Ferraz-Caetano  1 , Filipe Teixeira  2 , Maria Natália Dias Soeiro Cordeiro  1
Affiliations
Review

Systematic Development of Vanadium Catalysts for Sustainable Epoxidation of Small Alkenes and Allylic Alcohols

José Ferraz-Caetano et al. Int J Mol Sci. .

Abstract

The catalytic epoxidation of small alkenes and allylic alcohols includes a wide range of valuable chemical applications, with many works describing vanadium complexes as suitable catalysts towards sustainable process chemistry. But, given the complexity of these mechanisms, it is not always easy to sort out efficient examples for streamlining sustainable processes and tuning product optimization. In this review, we provide an update on major works of tunable vanadium-catalyzed epoxidations, with a focus on sustainable optimization routes. After presenting the current mechanistic view on vanadium catalysts for small alkenes and allylic alcohols' epoxidation, we argue the key challenges in green process development by highlighting the value of updated kinetic and mechanistic studies, along with essential computational studies.

Keywords: alkene epoxidation; allylic alcohol epoxidation; sustainable chemistry; vanadium catalysts.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Common commercial epoxides (from left to right): glycidol (oxiran-2-yl)methanol)—(a); ethylene oxide (oxirane)—(b); propylene oxide (2-methyloxirane)—(c).
Figure 2
Figure 2
Schematic representation of allylic alcohol epoxidation.
Figure 3
Figure 3
Graphical distribution of the possible epoxidation routes for small alkenes and allylic alcohol by oxidizing agents and catalysts.
Figure 4
Figure 4
Some examples of vanadium-based catalyst complexes [VO(acac)2] (a); vanadium(IV) complexes with Schiff base ligands (b); VO(porphyrin)-complexes (c); and [VO(OiPr)3] (d).
Figure 5
Figure 5
Schematic overview of the oxovanadium catalytic system for the epoxidation of olefins and allylic alcohols. Side reactions represent the inception of active complexes.
Figure 6
Figure 6
Proposed mechanism for the irreversible formation of an active epoxidation catalyst from [VO(acac)2] complex in the presence of acetic acid.
Figure 7
Figure 7
Mechanism outline for epoxidation Sharpless route (‡ = transition state) [34].
Figure 8
Figure 8
Mechanism outline for epoxidation Mimoun-type route (‡ = transition state) [61].
Figure 9
Figure 9
Mechanism outline for epoxidation Radical pathway route (‡ = transition state; · = radical) [57].
Figure 10
Figure 10
Schematic representation of the mechanism of epoxidation of alkenes with H2O2 catalyzed by a divanadium-substituted phosphotungstate [65].
Figure 11
Figure 11
Schematic representation of [VO(acac)2] catalyst inserted through the oxygen subunits of CAT1 [95].
Figure 12
Figure 12
Schematic representation of enantioselective asymmetric epoxidation of a meso secondary homoallylic alcohol with [VO(OiPr)3] as catalyst [55].
Figure 13
Figure 13
Epoxidation reaction scheme for oxovanadium-based complexes with olefins [29].
Figure 14
Figure 14
Structure of oxovanadium(IV) complexes used by Mohebbi [48].
Figure 15
Figure 15
Representation of oxo(peroxo)(corrolato)vanadium(V) for epoxidation of cycloalkenes using KHCO3 as a promoter [117].
Figure 16
Figure 16
Schematic representation of (pre-reaction) synthesis example of [VO(acac)2]-based active catalysts [29].
See this image and copyright information in PMC

References

    1. Meninno S., Lattanzi A. Epoxides: Small Rings to Play with under Asymmetric Organocatalysis. ACS Org. Inorg. Au. 2022;2:289–305. doi: 10.1021/acsorginorgau.2c00009. - DOI - PMC - PubMed
    1. Nielsen L.P.C., Jacobsen E.N. Aziridines and Epoxides in Organic Synthesis. Wiley-VCH; Weinheim, Germany: 2006. Catalytic Asymmetric Epoxide Ring-opening Chemistry; pp. 229–269.
    1. Padwa A., Murphree S. Epoxides and aziridines—A mini review. ARKIVOC. 2005;2006:6–33. doi: 10.3998/ark.5550190.0007.302. - DOI
    1. Molander G.A., Mautner K. Novel processes for stereoselective organic synthesis. Pure Appl. Chem. 1990;62:707–712. doi: 10.1351/pac199062040707. - DOI
    1. Bryliakov K.P. Catalytic Asymmetric Oxygenations with the Environmentally Benign Oxidants H2O2 and O2. Chem. Rev. 2017;117:11406–11459. doi: 10.1021/acs.chemrev.7b00167. - DOI - PubMed