Catalytic Cleavage of C(sp2)–C(sp2) Bonds with Rh-Carbynoids

Wang, Zhaofeng; Jiang, Liyin; Sarró, Pau; Suero, Marcos G.

doi:10.1021/jacs.9b08632

Cited by 64 publications

(58 citation statements)

References 52 publications

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“…Rhodium‐carbenoids can be generated from various precursors as diazo compounds, [80] cyclopropenes, [81] enynals/enynones [82] or substituted triazols [83] . Rhodium‐carbynoid was recently generated from hypervalent iodo‐derivative containing diazo moiety and its reactivity was studied in the reaction with alkenes [84] . Rhodium‐nitrenoids are typically generated from imidoiodinanes, which are prepared in situ by oxidation of amides using hypervalent iodine compounds or by decomposition of azides [85] or by α‐elimination reactions [86] .…”

Section: Applications Of Dirhodium(iiii) Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh2A4. These complexes have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, they act as Lewis acids to activate unsaturated bonds, serve as hydrogenation catalysts and participate in oxidation/reduction processes. Dirhodium paddlewheel complexes are composed of the Rh‐Rh backbone and four bridging anions, which surround the core. According to the application, the electrochemical potential of the Rh atom can be modulated, as can the geometry and physical and chemical properties of the metal complex. Dirhodium complexes can be prepared in one step from basic inorganic precursors or by post‐functionalization of the paddlewheel structures.

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Section: Applications Of Dirhodium(iiii) Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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“…Hypervalent iodoallyl intermediates have been proposed in sigmatropic [2,3] and [3,3] rearrangements . Reactive allylic cation intermediates were accessed recently using diazo‐substituted hypervalent iodine reagents by Suero . In our work, we now disclose a different approach based on the treatment of O‐VBX reagents with base and nucleophiles for the formation of C−O, C−N, and C−C bonds in allylic position.…”

Section: Methodsmentioning

confidence: 93%

Access to Vinyl Ethers and Ketones with Hypervalent Iodine Reagents as Oxy‐Allyl Cation Synthetic Equivalents

Declas

Waser

2020

Angewandte Chemie

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We report an Umpolung strategy of enol ethers to generate oxy‐allyl cation equivalents based on the use of hypervalent iodine reagents. Under mild basic conditions, the addition of nucleophiles to aryloxy‐substituted vinylbenziodoxolone (VBX) reagents, easily available in two steps from silyl alkynes, resulted in the stereoselective formation of substituted aryl enol ethers. The reaction was most efficient with phenols as nucleophiles, but preliminary results were also achieved for C‐ and N‐ nucleophiles. In absence of external nucleophiles, the 2‐iodobenzoate group of the reagent was transferred. The obtained aryl enol ethers could then be transformed into α‐difunctionalized ketones by oxidation. The described “allyl cation”‐like reactivity contrast with the well‐established “vinyl‐cation” behavior of alkenyl iodonium salts.

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“…Changing the order in which the two “masking” groups are released can be achieved by replacing the key photocatalyst with a transition‐metal catalyst. In 2019, the group of Suero manipulated a paddlewheel dirhodium complex and pseudo‐cyclic iodonio diazo reagents 70 for the first constructive scission of C(sp 2 )=C(sp 2 ) bonds in alkenes 69 , and inserted a monovalent carbon unit to transform alkenes into more substituted ones (Scheme ) . Instead of first releasing a monovalent iodoarene as under photochemical conditions (Scheme ), a highly electrophilic rhodium carbynoid intermediate R , which possesses carbene/carbocation behavior as a cationic carbyne equivalent, is generated from the Rh catalyst and the diazo moiety with the expulsion of nitrogen gas.…”

Section: Intramolecular Combinations To Form a Useful Reagentmentioning

confidence: 99%

Reactions between Diazo Compounds and Hypervalent Iodine(III) Reagents

Zhao

Shi

2020

Angewandte Chemie

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Site‐selective “cut and sew” transformations employing diazo compounds and hypervalent iodine(III) compounds involve the departure of leaving groups, a “cut” process, followed by a reorganization of the fragments by bond formation, a “sew” process. Bearing controllable cleavage sites, diazo compounds and hypervalent iodine(III) compounds play a critical role as versatile reagents in a wide range of organic transformations because their excellent nucleofugality allows for a large number of unusual reactions to occur. In recent years, the combination of diazo compounds and hypervalent iodine(III) reagents has emerged as a promising tool for developing new and valuable approaches, and has met considerable success. In this Minireview, this combination is systematically illustrated with recent advances in the field, with the aim of elaborating the synthetic utility and potential of this concept as a powerful strategy in organic synthesis.

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Catalytic Cleavage of C(sp²)–C(sp²) Bonds with Rh-Carbynoids

Cited by 64 publications

References 52 publications

Dirhodium(II,II) Paddlewheel Complexes

Dirhodium(II,II) Paddlewheel Complexes

Access to Vinyl Ethers and Ketones with Hypervalent Iodine Reagents as Oxy‐Allyl Cation Synthetic Equivalents

Reactions between Diazo Compounds and Hypervalent Iodine(III) Reagents

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