Progress in organocatalysis with hypervalent iodine catalysts

Singh, Fateh V.; Shetgaonkar, Samata E.; Krishnan, Manjula; Wirth, Thomas

doi:10.1039/d2cs00206j

Cited by 92 publications

(50 citation statements)

References 208 publications

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“…Effective hypervalent iodine(III)-catalyzed processes (for example, oxidative double C=C bond functionalization, oxidative cyclizations, CH-functionalization of carbonyl compounds, etc.) employing mainly peroxoacids or electric current as terminal oxidants were developed [139][140][141][142][143][144][145]. The key step in the catalytic cycle involving aryl iodides is the formation of iodine(III) species.…”

Section: Hypervalent Iodine 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: Hypervalent Iodine 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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“…8,9 Different chiral iodoarenes have been utilized as organocatalysts in several impressive stereoselective transformations. [10][11][12] Furthermore, relatively weak iodine-ligand bonds in HIRs allow their use in radical chemistry as well. 13 Homolysis of HIRs resulting from their photoactivation under UV mercury lamp has been studied since the late 80s.…”

Section: Introductionmentioning

confidence: 99%

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Narobe

Koenig

2023

Org. Chem. Front.

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“…The spirolactone framework is not only a potentially useful subunit in natural products and bioactive compounds, such as spiroindicumide A, spiroindicumide B, lagoditerpene E, norcrocrassinone, pathylactone, arteannuin B, petuniolide (C and E), and petunianine B (Figure ), but also plays a key role in developing more novel and versatile chiral auxiliaries for catalytic enantioselective oxidative dearomatization reactions. Recently, many research groups have reported chiral hypervalent iodine-catalyzed intramolecular spirolactonization. , In general, the hypervalent iodine-promoted dearomatization can be achieved at either ortho , or para , positions of the starting phenols, resulting in the formation of either 2,4-cyclohexadienones or 2,5-cyclohexadienones, respectively (Scheme ). To the best of our knowledge, the formation of a spirolactone ring moiety at the meta -position of phenol via a dearomatization process has been rarely accomplished.…”

Section: Introductionmentioning

confidence: 99%

Polyhalogenation-Facilitated Spirolactonization at the meta-Position of Phenols

Cao

et al. 2023

J. Org. Chem.

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A novel dearomative spirolactonization/polyhalogenation of phenols that employs hypervalent iodine PhICl2 (iodobenzene dichloride) as both an oxidant and chlorine source with an indispensable base, or only using NBS (N-bromosuccinimide) without any additives, is presented. Halide participations are a vital factor in the cascade reaction of 3′-hydroxy-[1,1′-biphenyl]-2-carboxylic acids with good selectivities and reactivities and induced the rapid constructions of multiple C–halogen bonds and directional CO bonds in a one-step operation under mild conditions. In gaining a good understanding of the mechanism, the increase in number of bromine atoms was inferred rationally from the spirolactonization process, assisted by DFT calculations and high-resolution mass spectrometry. Mechanistic experiments suggest that the formation of a stable carbocation intermediate plays a great role in the migration of oxygen to spirolactonization.

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Progress in organocatalysis with hypervalent iodine catalysts

Abstract: Hypervalent iodine compounds as environmentally friendly and relatively inexpensive reagents have properties similar to transition metals.

Cited by 92 publications

References 208 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

Transformations based on direct excitation of hypervalent iodine(iii) reagents

Polyhalogenation-Facilitated Spirolactonization at the meta-Position of Phenols

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