Rh(III)-Catalyzed Three-Component <i>Syn</i>-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

Lee, Sumin; Rovis, Tomislav

doi:10.1021/acscatal.1c02406

Cited by 41 publications

(26 citation statements)

References 43 publications

(32 reference statements)

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“…Based on the above experimental results and the aforementioned literatures, [7b,8a, 18] a feasible mechanistic proposal was outlined in Scheme 5. Initially, the coordination of dioxazolones 1 to rhodium catalyst afforded the highly active rhodium nitrene intermediate A by releasing one molecule of CO 2 .…”

Section: Resultsmentioning

confidence: 90%

Rh(III)‐CatalyzedN‐Arylation of Alkyl Dioxazolones with Arylboronic Acids for the Synthesis ofN‐Aryl Amides

et al. 2022

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Herein, a method for N‐aryl amides preparation has been established through Rh(III)‐catalyzed C(sp2)−N cross‐coupling reactions of alkyl dioxazolones with arylboronic acids, heterocyclic boronic acid, and alkenyl boronic acid. This efficient and straightforward catalytic approach was featured with broad substrate scope (38 examples), good functional group compatibility, high yields (up to 99 %), and is suitable for late‐stage modification of drug molecular structures. The possible mechanism hypothesis was also accomplished.

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Section: Resultsmentioning

confidence: 90%

Rh(III)‐CatalyzedN‐Arylation of Alkyl Dioxazolones with Arylboronic Acids for the Synthesis ofN‐Aryl Amides

et al. 2022

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“…Transfer of an amino group into organic compounds by harnessing the electrophilic reactivity of transient metallonitrene intermediates is an appealing synthetic route to a diverse range of aminated scaffolds. − Indeed, several notable examples have been revealed toward the α-amination of carbonyl compounds via the metal-nitrenoid intermediacy. − In this line, we recently reported an intermolecular α-amidation of 1,3-dicarbonyls by designing a Cp*(LX)Ir(III) catalyst system bearing κ 2 - N,O ligands. , The high catalytic reactivity was attributed to the modulated electrophilic nature of the putative Ir-nitrenoids to effectively interact with nucleophilic enols in situ obtained from the 1,3-dicarbonyl compounds. As a natural extension, we wondered whether this amidation approach could also be applied to the α-amidation of esters.…”

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confidence: 99%

Iridium-Catalyzed Amidation of In Situ Prepared Silyl Ketene Acetals to Access α-Amino Esters

et al. 2022

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Disclosed herein is a convenient Ir-catalyzed amidation of esters to access α-amido esters. Initially prepared silyl ketene acetals are directly employed, without separate purification, for subsequent amidation with an oxycarbonylnitrenoid precursor using the Cp*(LX)Ir(III) catalyst. The α-amidation was facile for both α-aryl and α-alkyl esters. Density functional theory studies revealed that the generation of a putative Ir-nitrenoid is facilitated by the chelation of the countercation additive during the N–O bond cleavage of the nitrene precursor.

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“…Over the last years, 1,4,2-dioxazol-5-ones 2 have evolved into extremely practical acyl amino sources, which are readily available from carboxylic acids. ,− ,− Along these lines, fluorinated amide 6b (49%) as well as n -alkyl substituted amides 6c , 6d (61–67%) are successfully incorporated in the amino hydroxylation protocol. Furthermore, sterically more demanding groups such as α-tertiary amides 6e – g (37–61%) and benzyl substituents ( 6h , 44%) are compatible.…”

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confidence: 99%

Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones

Burg

Rovis

2022

ACS Catal.

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We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- and N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37–91% yield). Previous attempts to functionalize the internal double bond rested on the use of plain alcoholic solvents as nucleophilic coupling partners thus dramatically limiting the scope of this transformation. We have now identified hexafluoroisopropanol as a non-nucleophilic solvent that allows the use of diverse nucleophiles and greatly expands the scope, including an unprecedented amino hydroxylation to selectively install valuable, unprotected β-amino alcohols across 1,3-dienes. Moreover, various elaborate alcohols prove to be compatible providing unique access to complex organic molecules. Finally, this method is employed in a series of intramolecular reactions to deliver valuable nitrogen heterocycles as well as γ- and δ-lactones.

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Rh(III)-Catalyzed Three-Component Syn-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

Cited by 41 publications

References 43 publications

Rh(III)‐CatalyzedN‐Arylation of Alkyl Dioxazolones with Arylboronic Acids for the Synthesis ofN‐Aryl Amides

Rh(III)‐CatalyzedN‐Arylation of Alkyl Dioxazolones with Arylboronic Acids for the Synthesis ofN‐Aryl Amides

Iridium-Catalyzed Amidation of In Situ Prepared Silyl Ketene Acetals to Access α-Amino Esters

Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones

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