Ring Opening Reactions of Epoxides. A Review

Thirumalaikumar, M.

doi:10.1080/00304948.2021.1979357

Cited by 29 publications

(11 citation statements)

References 174 publications

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“…Epoxides are a valuable class of compounds across the pharmaceutical and fragrance industries. , They can be found in medicinal compounds such as carfilzomib (an anticancer agent) and troleandomycin (a macrolide antibiotic), though they are more often employed as key building blocks in the syntheses of fine chemical products. , The reactivity of epoxides toward a broad range of nucleophiles makes them versatile intermediates. , …”

Section: Introductionmentioning

confidence: 99%

“…3,4 The reactivity of epoxides toward a broad range of nucleophiles makes them versatile intermediates. 5,6 The oxidation of an alkene is an effective route for the preparation of epoxides; however, oxidations are often challenging due to the environmental and economic problems associated with traditional, stoichiometric oxidizing agents. 6 For example, the storage, transport, and use of 3-chloroperoxybenzoic acid (mCPBA) on a large scale has been highlighted as a challenge for some time due to the risk of explosion.…”

Section: ■ Introductionmentioning

confidence: 99%

“… 3 , 4 The reactivity of epoxides toward a broad range of nucleophiles makes them versatile intermediates. 5 , 6 …”

Section: Introductionmentioning

confidence: 99%

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Continuous Flow Epoxidation of Alkenes Using a Homogeneous Manganese Catalyst with Peracetic Acid

Ryan

Dempsey

Smyth

et al. 2023

Org. Process Res. Dev.

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Epoxidation of alkenes is a valuable transformation in the synthesis of fine chemicals. Described herein are the design and development of a continuous flow process for carrying out the epoxidation of alkenes with a homogeneous manganese catalyst at metal loadings as low as 0.05 mol%. In this process, peracetic acid is generated in situ and telescoped directly into the epoxidation reaction, thus reducing the risks associated with its handling and storage, which often limit its use at scale. This flow process lessens the safety hazards associated with both the exothermicity of this epoxidation reaction and the use of the highly reactive peracetic acid. Controlling the speciation of manganese/2-picolinic acid mixtures by varying the ligand:manganese ratio was key to the success of the reaction. This continuous flow process offers an inexpensive, sustainable, and scalable route to epoxides.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Continuous Flow Epoxidation of Alkenes Using a Homogeneous Manganese Catalyst with Peracetic Acid

Ryan

Dempsey

Smyth

et al. 2023

Org. Process Res. Dev.

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“…Synthetic approaches towards such drugs as atazanavir (HYV protease inhibitor), linezolid (antibiotic), diltiazem (antihypertensive drug), and a number of others include transformations of oxirane moiety [ 6 ]. Reactions of oxirane ring opening are widely used as a regio- and stereoselective approach to polyfunctional and heterocyclic compounds, and novel reactions and synthetic procedures employing oxiranes are still being developed [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ]. The presence of two or more oxirane moieties in a molecule creates the opportunity for a straightforward synthesis of polyfunctional compounds, and for the use of such a molecule as a linker in the construction of multivalent ligands.…”

Section: Introductionmentioning

confidence: 99%

Bis(oxiranes) Containing Cyclooctane Core: Synthesis and Reactivity towards NaN3

et al. 2022

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Reactions of oxirane ring opening provide a powerful tool for regio- and stereoselective synthesis of polyfunctional and heterocyclic compounds, widely used in organic chemistry and drug design. Cyclooctane, alongside other medium-sized rings, is of interest as a novel molecular platform for the construction of target-oriented leads. Additionally, cyclooctane derivatives are well known to be prone to transannular reactions, which makes them a promising object in the search for novel approaches to polycyclic structures. In the present work, a series of cyclooctanediones was studied in Corey-Chaykovsky reactions, and novel spirocyclic bis(oxiranes) containing cyclooctane core, namely, 1,5-dioxadispiro[2.0.2.6]dodecane and 1,8-dioxadispiro[2.3.2.3]dodecane, were synthesized. Ring opening of the obtained bis(oxiranes) upon treatment with sodium azide was investigated, and it was found that the reaction path is determined by the reciprocal orientation of oxygen atoms in the oxirane moieties. Diastereomers of the bis(oxiranes) with cis-orientation underwent independent ring opening, supplying corresponding diazidodiols, while in the case of stereoisomers with trans-orientation, domino-like reactions occurred, including intramolecular nucleophilic attack and the formation of a novel three- or six-membered O-containing ring. Summarily, a straightforward approach to polyfunctional compounds containing cyclooctane or oxabicyclo[3.3.1]nonane cores, employing bis(oxiranes), was elaborated.

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“…Both its formation and ring opening have led to pioneering discoveries and highly useful synthetic methods alike. In terms of ring opening, − most documented cases involve scission of the C–O bond (Figure ), as the attacking reagent is generally nucleophilic in character . Instances of nucleophilic C–C scission are rare, and limited to epoxides containing electron-withdrawing groups .…”

mentioning

confidence: 99%

C–C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications

Holt,

Garrison,

Rowshanpour

et al. 2023

J. Org. Chem.

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In this note, we explore a unique reactivity pattern that involves a rare radical-based C−C bond scission of epoxides followed by demethylenation. The reaction is accomplished by Selecfluor and its radical dication working in tandem; a mechanism supported by experiment and DFT calculations is proposed that involves the generation and identification of a key reactive intermediate. The reaction seems to be fairly general for 1,1-disubstituted epoxides.

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Ring Opening Reactions of Epoxides. A Review

Cited by 29 publications

References 174 publications

Continuous Flow Epoxidation of Alkenes Using a Homogeneous Manganese Catalyst with Peracetic Acid

Continuous Flow Epoxidation of Alkenes Using a Homogeneous Manganese Catalyst with Peracetic Acid

Bis(oxiranes) Containing Cyclooctane Core: Synthesis and Reactivity towards NaN3

C–C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications

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