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2.5.2.4 Iron-Catalyzed Epoxidation

DOI: 10.1055/sos-SD-225-00063

Vicens, L.; Borrell, M.; Costas, M.Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (20171135.

Epoxidation is a fundamental and well-established reaction in organic synthesis and epoxides have a very versatile reactivity that makes them excellent starting points for a number of reactions;[‌62‌] however, current methods for epoxidation produce significant amounts of byproducts. In addition, because of the rich reactivity of epoxides, chemoselectivity remains a critical aspect in epoxidations when carried out with aggressive oxidants and under acidic conditions. These aspects fuel the interest for the discovery of more efficient and sustainable methods.[‌63‌] Inspired by oxygen atom transfer reactions performed by iron enzymes, an active research line has been focused on developing iron-based catalysts.[‌27‌,‌64‌] Ideally, these catalysts should employ molecular oxygen or hydrogen peroxide as oxidant, producing water as the only waste product. In these reactions, it is presumed that the reaction of the iron catalyst with the oxidant resembles that occurring in reactions taking place in non-heme iron enzymes, forming high-valent iron oxo intermediates via O—O bond lysis reactions.

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M8 M8 M8 Meeee (%) Mee
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M8 M8 M8 Meeee (%) Mee
(MM8)8 M 88 [‌88‌]
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Meeeeeeeeee 88M

M8 M8 M8 Meeee (%) Mee
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Me M eeeee 88–88 [‌88‌]
MM=MM(MM8)8 M 88 [‌88‌]
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Me M Me 88 [‌88‌]
Me M MM8MM8 88–88 [‌88‌]
Me M (MM8)8Me 88 [‌88‌]

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M8 M8 M8 M8 Me8 Meeee (%) Mee
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Me M Me Me Me 88 [‌88‌]
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Meeeeeeeeee 88M

M8 M8 Meeee (%) Mee
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MM=MM(MM8)8 88 [‌88‌]
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Meeeeeeeeee 88M

M8 M8 M8 Meeee (%) Mee
eeee M eeee 88–88 [‌88‌]
Me eeeee eeeee 88–88 [‌88‌]

Meeeeeeeeee 88M

M8 M8 M8 Meeee (%) Mee
(MM8)8Me M M 88 [‌88‌]
Me M M 88 [‌88‌]
Me Me M 88 [‌88‌]
(MM8)8 M 88 [‌88‌]
Me M MMM8 88–88 [‌88‌]
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Meeeeeeeeee 88M

M8 M8 Meeee (%) Mee
(MM8)8 888 [‌88‌]
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(MM8)8Me M 88 [‌88‌]

Meeeeeeeeee 88M

Meeeeeeeee Meeee (%) Mee
88 (8 eee%), MeMM (8.8 eeeee), M8M8 (8 eeeee), MeMM, ee, 88 eee 88 [‌88‌]
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Meeeeeeeee Meeee (%) Mee
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Meeeeeeeeee 88M

M8 M8 M8 Me(MMe)8 (eee%) M8M8 (Meeee) Meeeeee Meeee (%) Mee
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References