Shi Epoxidation: A Great Shortcut to Complex Compounds

Feng, Xiujuan; Du, Haifeng

doi:10.1002/cjoc.202000744

Cited by 8 publications

(5 citation statements)

References 142 publications

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“…Dioxiranes formed from ketones and hydroperoxides are electrophilic oxygen transferring agents used in epoxidation (including asymmetric variants) [131,132], CH-hydroxylation, and other oxidation processes [132][133][134]. Fluorinated substituents in the ketone molecule are used to achieve higher electrophilicity and reactivity.…”

Section: Dioxirane and Oxaziridine Catalysismentioning

confidence: 99%

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Lopat’eva¹,

Krylov²,

Lapshin³

et al. 2022

Beilstein J. Org. Chem.

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Organocatalysis is widely recognized as a key synthetic methodology in organic chemistry. It allows chemists to avoid the use of precious and (or) toxic metals by taking advantage of the catalytic activity of small and synthetically available molecules. Today, the term organocatalysis is mainly associated with redox-neutral asymmetric catalysis of C–C bond-forming processes, such as aldol reactions, Michael reactions, cycloaddition reactions, etc. Organophotoredox catalysis has emerged recently as another important catalysis type which has gained much attention and has been quite well-reviewed. At the same time, there are a significant number of other processes, especially oxidative, catalyzed by redox-active organic molecules in the ground state (without light excitation). Unfortunately, many of such processes are not associated in the literature with the organocatalysis field and thus many achievements are not fully consolidated and systematized. The present article is aimed at overviewing the current state-of-art and perspectives of oxidative organocatalysis by redox-active molecules with the emphasis on challenging chemo-, regio- and stereoselective CH-functionalization processes. The catalytic systems based on N-oxyl radicals, amines, thiols, oxaziridines, ketone/peroxide, quinones, and iodine(I/III) compounds are the most developed catalyst types which are covered here.

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Section: Dioxirane and Oxaziridine Catalysismentioning

confidence: 99%

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Lopat’eva¹,

Krylov²,

Lapshin³

et al. 2022

Beilstein J. Org. Chem.

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“…5,6 Since then, several other ketones have been prepared to achieve better selectivity and yields. [7][8][9][10][11] Small ring heterocycles, such as epoxides, are present in several natural compounds 12,13 and represent highly versatile building blocks, frequently involved in the synthesis of pharmaceuticals and bioactive products. [14][15][16] In addition, carbohydrates possess several hydroxyl groups, which is a unique and valuable characteristic to serve as binding sites, being easily converted to other functional groups based on the structural requirements for catalyst development.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Shi-type epoxidation with 3-oxo-4,6-O-benzylidene pyranoside catalysts: unveiling the role of carbohydrate skeletons

Imperio,

Valloni,

Caprioglio

et al. 2024

RSC Adv.

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“…Asymmetric epoxidation of alkenes is an attractive and important approach to access chiral epoxides which are extremely versatile synthetic intermediates. − Great success has been achieved via the development of a variety of catalytic systems, involving chiral metal catalysis and organocatalysis, − such as well-known Sharpless epoxidation and Shi epoxidation . Among these methods, the catalysts based on the late 3d-transition metals, which are inspired by the oxidation reactions featured in enzymatic processes, have drawn much attention (Figure a).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Epoxidation of Alkenes Catalyzed by a Cobalt Complex

Jiang

et al. 2023

J. Am. Chem. Soc.

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Asymmetric epoxidation of alkenes catalyzed by nonheme chiral Mn−O and Fe−O catalysts has been well established, but chiral Co−O catalysts for the purpose remain virtually undeveloped due to the oxo wall. Herein is first reported a chiral cobalt complex to realize the enantioselective epoxidation of cyclic and acyclic trisubstituted alkenes by using PhIO as the oxidant in acetone, wherein the tetraoxygen-based chiral N,N′-dioxide with sterically hindered amide subunits plays a crucial role in supporting the formation of the Co−O intermediate and enantioselective electrophilic oxygen transfer. Mechanistic studies, including HRMS measurements, UV−vis absorption spectroscopy, magnetic susceptibility, as well as DFT calculations, were carried out, confirming the formation of Co−O species as a quartet Co(III)-oxyl tautomer. The mechanism and the origin of enantioselectivity were also elucidated based on control experiments, nonlinear effects, kinetic studies, and DFT calculations.

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Shi Epoxidation: A Great Shortcut to Complex Compounds

Cited by 8 publications

References 142 publications

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Stereoselective Shi-type epoxidation with 3-oxo-4,6-O-benzylidene pyranoside catalysts: unveiling the role of carbohydrate skeletons

Asymmetric Epoxidation of Alkenes Catalyzed by a Cobalt Complex

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