Divergent Catalytic Approach from Cyclic Oxime Esters to Nitrogen-Containing Heterocycles with Group 9 Metal Catalysts

Shimbayashi, Takuya; Matsushita, Gaku; Nanya, Atsushi; Eguchi, Akira; Okamoto, Kazuhiro; Ohe, Kouichi

doi:10.1021/acscatal.8b01646

Cited by 48 publications

(25 citation statements)

References 107 publications

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“…[78] Very recently,w er eported the rhodium-and cobalt-catalyzed transformationo fi soxazolones into 2H-pyrroles and azabicyclo[3.1.0]hex-2-enes,r espectively. [79] Ther hodiumc omplex bearing an electron-rich phosphine ligand catalyzed the formation of the 2H-pyrrolep roducts in good yields (Scheme 72). This was in sharpc ontrastt op alladium catalysis, for which an electron-deficient phosphine ligand workedw ell.…”

Section: Isoxazolonesmentioning

confidence: 99%

“…Very recently, we reported the rhodium‐ and cobalt‐catalyzed transformation of isoxazolones into 2 H ‐pyrroles and azabicyclo[3.1.0]hex‐2‐enes, respectively . The rhodium complex bearing an electron‐rich phosphine ligand catalyzed the formation of the 2 H ‐pyrrole products in good yields (Scheme ).…”

Section: Decarboxylative Generation Of Nitrenoid Species From Cyclic mentioning

confidence: 99%

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Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Shimbayashi

Sasakura

Eguchi

et al. 2018

Chemistry A European J

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113

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Nitrene-transfer reactions have been a powerful synthetic method for direct incorporation of nitrogen atoms into organic molecules. Discovery of novel nitrene-transfer reactions has been dominantly supported by not only the improvement in transition-metal catalysts but also by the employment of novel precursors of nitrenoids. Since the pioneering works utilizing organic azides or iminoiodinanes as practical synthetic tools for nitrogen-containing compounds were reported, a new approach using various N-heterocycles containing strain energy or a weak bond has emerged. In this review, we briefly summarize the history of nitrene-transfer chemistry from the viewpoint of its precursors. In particular, the use of N-heterocycles such as 2H-azirines, 1,4,2-dioxazol-5-ones, 1,2,4-oxadiazol-5-ones, isoxazol-5(4H)-ones, and isoxazoles are comprehensively described, showing the recent remarkable progress in this chemistry.

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Section: Isoxazolonesmentioning

confidence: 99%

Section: Decarboxylative Generation Of Nitrenoid Species From Cyclic mentioning

confidence: 99%

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Shimbayashi

Sasakura

Eguchi

et al. 2018

Chemistry A European J

Self Cite

113

View full text Add to dashboard Cite

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“…The P–C sp 2 and P–C sp 3 products 3a , 4a , and 4a′ were further transformed (Scheme ). Reduction of 3a with NaBH 4 in EtOH furnished the corresponding hydroxymethylene 10 in 45% yield . Hydrogenation of the exocyclic double bond of 3a was carried out using Pd/C as a catalyst to give 1,3- syn -disubstituted spiroindanoxazolone 11 in 72% yield .…”

Section: Resultsmentioning

confidence: 99%

Highly Regioselective Tandem Reaction of Ene-Yne-Oxazolones Induced by H-Phosphonates: Construction of Phosphinylindane Derivatives

et al. 2021

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A highly regioselective divergent approach for the phosphine-containing indane/indene derivatives from the ene-yneoxazolone precursors was reported. An insight into the reaction mechanism involving the phospha-1,4-addition followed by 5-exodig ring closure with a concomitant C−P/C−C bond formation was also proposed. This promising protocol utilized Hphosphonate as the phosphonating reagent in a silver-catalyzed or base-mediated cascade cyclization to construct the corresponding phosphorylated spiroindenoxazolones and amidoindenes, respectively, in good yields (up to 88% yield).

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“…Some transition metals have horizontal and vertical similarities in the periodic table as a result of their similar electronic configurations. However, they can also exhibit different behaviors under similar reaction conditions . Therefore, when an unusual reaction is discovered, the elucidation of the underlying mechanism is essential to understand the characteristic reactivity of the transition metal.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies of the Pd- and Pt-Catalyzed Selective Cyclization of Propargyl/Allenyl Complexes

2021

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Following the discovery of an unusual transitionmetal-catalyzed reaction, the elucidation of the underlying mechanism is essential to understand the characteristic reactivity of the metal. We previously reported a synthetic method for tricyclic indoles using Pt-catalyzed Friedel−Crafts-type C−H coupling. In this reaction, the Pt catalyst selectively formed a seven-membered ring, but the Pd catalyst only afforded a six-membered ring. However, the reasons for the different selectivities caused by Pd and Pt were unclear. We performed density functional theory (DFT) calculations and experimental studies to reveal the origin of the different behaviors of the two metals. The calculations revealed that the formation of the six-and seven-membered rings proceeds via η 1 -allenyl and η 3propargyl/allenyl complexes, respectively. A molecular orbital analysis of the η 3 -propargyl/allenyl complex revealed that, for the platinum complex, the energy required to convert the unoccupied molecular orbital on the reactive carbon into the lowest unoccupied molecular orbital (LUMO) was lower than that for the palladium complex. In addition, DFT calculations revealed that the combination of platinum and bis[2-(diphenylphosphino)phenyl] ether (DPEphos) reduced the activation energy of the sevenmembered cyclization in comparison with palladium or PPh 3 . Additional experimental studies, including NMR studies and stoichiometric reactions, support the aforementioned examination.

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Divergent Catalytic Approach from Cyclic Oxime Esters to Nitrogen-Containing Heterocycles with Group 9 Metal Catalysts

Cited by 48 publications

References 107 publications

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Highly Regioselective Tandem Reaction of Ene-Yne-Oxazolones Induced by H-Phosphonates: Construction of Phosphinylindane Derivatives

Mechanistic Studies of the Pd- and Pt-Catalyzed Selective Cyclization of Propargyl/Allenyl Complexes

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