Iridium- and Rhodium-Catalyzed Directed C–H Heteroarylation of Benzaldehydes with Benziodoxolone Hypervalent Iodine Reagents

Grenet, Erwann; Waser, Jérôme

doi:10.1021/acs.orglett.8b00337

Cited by 33 publications

(19 citation statements)

References 49 publications

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“…Then, metallocycle undergo oxidative addition with HIR gives high valent metal intermediate. In final step, reductive elimination and ligand exchange regenerates the metal acetate complex [77] …”

Section: Transformations Involving Hypervalent Iodine Reagents and 2 ...mentioning

confidence: 99%

“…The mechanistic cycle involves the following steps – (i) the active form of catalyst is generated by ligand exchange with potassium acetate; (ii) Active catalyst adds to salicylaldehyde to give metallacycle having iridium centre; (iii) Further, oxidative addition occurs by addition of indoleBX i. e . Rh(III) centre oxidizes to Rh(V) and indoleBX moiety is added; (IV) In the final step, reductive elimination and ligand exchange gives desired product and active catalyst is regenerated [115] …”

Section: Transformations Involving Hypervalent Iodine Reagents and 3r...mentioning

confidence: 99%

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Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

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This review outlines the progress over recent years in the reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium and cobalt. This approach enables organic transformations complimentary to traditional manifolds. Hypervalent iodine reagents play a preeminent role in organic chemistry due to their versatile reactivity, heteroatom ligands and mild reaction conditions. These reagents in combination of transition metal compounds are used in many synthetically useful organic reactions such as oxidation, rearrangement, amination, halogenation, amidation, ring-opening, cyclization and CÀ H and CÀ C functionalization reactions, etc. which are discussed here. Combination with Cobalt 2.3. Reactions of Hypervalent Iodine Reagents with Copper 2.4. Reactions of Hypervalent Iodine Reagents in Combination with Nickel 2.5. Reactions of Hypervalent Iodine Reagents in Combination with Zinc 3. Transformations Involving Hypervalent Iodine Reagents and 2 nd Transition Series Metals 3.1. Reactions of Hypervalent Iodine Reagents in Combination with Ruthenium 3.2. Reactions of Hypervalent Iodine Reagents in Combination With Rhodium 3.3. Reactions of Hypervalent Iodine Reagent in Combination With Palladium 3.4. Reactions of Hypervalent Iodine Reagents in Combination with Silver 4. Transformations Involving Hypervalent Iodine Reagents and 3rd Transition Series Metals 4.1. Reactions of Hypervalent Iodine Reagents in Combination with Rhenium 4.2. Reactions of Hypervalent Iodine Reagents in Combination with Iridium 4.3. Reactions of Hypervalent Iodine Reagents in Combination with Platinum 4.4. Reactions of Hypervalent Iodine Reagents in Combination with Gold 5. Conclusion

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Section: Transformations Involving Hypervalent Iodine Reagents and 2 ...mentioning

confidence: 99%

Section: Transformations Involving Hypervalent Iodine Reagents and 3r...mentioning

confidence: 99%

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

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“…67 Finally, the method could be extended to ortho-hydroxy and amido benzaldehydes using either a Rh(III) or an Ir(III) catalyst (Scheme 35d, products 71-73). 68 None of these transformations was successful using the corresponding aryl iodides or iodonium salts.…”

Section: Metal-catalyzed C-h Functionalization With Indolebxs and Pyrmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents: Enabling Tools for Bond Disconnection via Reactivity Umpolung

2018

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Conspectus The efficient synthesis of organic compounds is an important field of research, which sets the basis for numerous applications in medicine or materials science. Based on the polarity induced by functional groups, logical bond disconnections can be deduced for the elaboration of organic compounds. Nevertheless, this classical approach makes synthesis rigid, as not all bond disconnections are possible. The concept of Umpolung has been therefore introduced: by inverting the normal polarity of functional groups, new disconnections become possible. Among the tools for achieving Umpolung, hypervalent iodine reagents occupy a privileged position. The electrophilicity of the iodine atom and the reactivity of the hypervalent bond allow access to electrophilic synthons starting from nucleophiles. Nevertheless, some classes of hypervalent iodine reagents can be too unstable for many applications, in particular involving metal catalysis. In this context, cyclic hypervalent iodine reagents, especially benziodoxolones (BXs), have been known for a long time to be more stable than their acyclic counterparts, yet their synthetic potential had not been fully exploited. In this Account, we report our efforts since 2008 on the use of BX reagents in the development of new transformations in organic synthesis, which showed for the first time their versatility as synthetic tools. Our work started with electrophilic alkynylation, as alkynes are one of the most important functional groups in organic chemistry, but are usually introduced as nucleophiles. We used ethynylbenziodoxolones (EBXs) in the direct alkynylation of nucleophiles, such as keto esters, thiols, or phosphines. The reagents could then be applied to the gold- and palladium-catalyzed alkynylation of C–H bonds on (hetero)arenes, leading to a more efficient alternative to the Sonogashira reaction. More complex reactions were then developed with formations of several bonds in a single transformation. Gold- and platinum-catalyzed cyclization/alkynylation domino processes gave access to new types of alkynylated heterocycles. Multifunctionalization of olefins became possible through intramolecular oxy- and amino-alkynylations. (Enantioselective) copper-catalyzed oxy-alkynylation of diazo compounds led to stereocenters with perfect atom economy. Finally, EBXs were also used for the alkynylation of radicals generated under photoredox conditions. Since 2013, we then extended the use of BX reagents to other transformations. Azidobenziodoxol(on)ess (ABXs) were used in the azidation of keto esters, enol silanes, and styrenes. New more stable derivatives were introduced. Cyanobenziodoxolones (CBXs) enabled the cyanation of stabilized enolates, thiols, and radicals. Finally, new BX reagents were developed for the Umpolung of indoles and pyrroles. They could be used in metal-catalyzed directed C–H functionalizations, as well as in Lewis acid mediated oxidative coupling to give functionalized bi(hetero)arenes. In the past decade, our group and others have shown that BX reag...

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“…Bis‐arylated by product 8 was also observed in 17 % yield. Interestingly, only C2 functionalized indole 7 a was obtained starting from C3‐substituted indoleBX 2 a , whereas C3‐substituted products were formed when using transition metal catalysis –…”

Section: Figurementioning

confidence: 99%

Metal‐Free Oxidative Cross Coupling of Indoles with Electron‐Rich (Hetero)arenes

Caramenti

Nandi

Waser

2018

Chemistry A European J

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A new method for the synthesis of bi-heteroaryls is reported, based on the umpolung of indoles with benziodoxol(on)e hypervalent iodine reagents (IndoleBX). The oxidative coupling of IndoleBX with an equimolar amount of electron-rich benzenes, indoles, pyrroles, and thiophenes proceeded under mild transition-metal-free conditions. Functionalized non-symmetrical bi-indolyl heterocycles were accessed efficiently. Introduction of a new type of C2-substituted indole benziodoxole reagents further allowed extending the scope of the reaction to NH unprotected and C3-alkylated indoles. The obtained bi-heterocycles are important building blocks in synthetic and medicinal chemistry, and could be easily transformed into more complex heterocyclic systems.

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Iridium- and Rhodium-Catalyzed Directed C–H Heteroarylation of Benzaldehydes with Benziodoxolone Hypervalent Iodine Reagents

Cited by 33 publications

References 49 publications

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

Cyclic Hypervalent Iodine Reagents: Enabling Tools for Bond Disconnection via Reactivity Umpolung

Metal‐Free Oxidative Cross Coupling of Indoles with Electron‐Rich (Hetero)arenes

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