Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

Abstract

Hypervalent iodine(III) reagents have been well-developed and widely utilized in functionalization of alkenes, however, generally either stoichiometric amounts of iodine(III) reagents are required or stoichiometric oxidants such as mCPBA are employed to in situ generate iodine(III) species. In this review, recent developments of hypervalent iodine(III)-catalyzed functionalization of alkenes and asymmetric reactions using a chiral iodoarene are summarized.

Enantioselective, Catalytic Vicinal Difluorination of Alkenes

“…With the rapid expansion of drug discovery into 3D chemical space, enabling technologies for the efficient generation of stereochemically defined, fluorinated motifs from feedstock precursors will be of increasing importance. Cognisant of the prominence of trifluoromethylated aryl ring systems (ArCF 3 ) in contemporary medicinal chemistry, we sought to validate an enantioselective catalytic vicinal difluorination of styrenes through an I I /I III manifold . This catalysis platform has proven to be particularly competent for the direct fluorination of π‐bonds, often enantioselectively…”

Elektrochemischer Durchlaufgenerator für hypervalente Iodreagenzien: Synthetische Anwendungen

“…[1] Ihre starke Fluchtgruppenreaktivitätu nd ihr elektrophiler Charakter machen sie zu hervorragenden Kandidaten fürdie Durchführung selektiver Oxidationen, einschließlich oxidativer Umlagerungen, [2] der Difunktionalisierung von Alkenen und Cyclopropanen, [3] oxidativer C-C-, C-Heteroatom-und Heteroatom-Heteroatom-Kupplungen sowie der Dearomatisierung von Phenolen. [1] Ihre starke Fluchtgruppenreaktivitätu nd ihr elektrophiler Charakter machen sie zu hervorragenden Kandidaten fürdie Durchführung selektiver Oxidationen, einschließlich oxidativer Umlagerungen, [2] der Difunktionalisierung von Alkenen und Cyclopropanen, [3] oxidativer C-C-, C-Heteroatom-und Heteroatom-Heteroatom-Kupplungen sowie der Dearomatisierung von Phenolen.…”

“…Hypervalente Iodverbindungen sind effiziente und vielseitige Reagenzien mit zahlreichen Anwendungen in der modernen organischen Synthese. [1] Ihre starke Fluchtgruppenreaktivitätu nd ihr elektrophiler Charakter machen sie zu hervorragenden Kandidaten fürdie Durchführung selektiver Oxidationen, einschließlich oxidativer Umlagerungen, [2] der Difunktionalisierung von Alkenen und Cyclopropanen, [3] oxidativer C-C-, C-Heteroatom-und Heteroatom-Heteroatom-Kupplungen sowie der Dearomatisierung von Phenolen. [4] Hypervalente Iod-Reagenzien erlauben milde Reaktionsbedingungen und weisen geringe Toxizitäten auf,weshalb sie als umweltfreundliche Reagenzien Alternativen zu Schwermetalloxidationsmitteln bieten.…”

Continuous‐Flow Electrochemical Generator of Hypervalent Iodine Reagents: Synthetic Applications

“…Hypervalent iodine compounds are efficient and versatile reagents with numerous applications in modern organic synthesis. [1] Their strong leaving-group ability and electrophilic nature make them great candidates for achieving selective oxidative transformations,i ncluding oxidative rearrangements, [2] difunctionalizations of alkenes and cyclopropanes, [3] oxidative carbon-carbon, carbon-heteroatom, and heteroatom-heteroatom couplings,a nd dearomatizations of phenols. [4] Hypervalent iodine reagents are used under mild reaction conditions and of low toxicity,w hich makes them environmentally friendly reagents that are often used as an alternative to heavy-metal oxidants.However, their synthesis from iodine(I) compounds usually requires as toichiometric amount or an excess of chemical oxidants,s uch as peroxides (e.g.,h ydrogen peroxide, meta-chloroperbenzoic acid, peracetic acid, ), Selectfluor ,o rO xone ,m aking the process tedious and less convenient.…”