On the Reactivity Toward Ketones of New Methyl Amino Complexes of Rh(III) and Ag(I). Synthesis of Ortho-Rhodiated Acetophenone Methyl Imine Complexes

Vicente, José; Chicote, Mariá‐Teresa; Vicente-Hernandez, Inmaculada; Bautista, Delia

doi:10.1021/ic700963h

Cited by 12 publications

(28 citation statements)

References 25 publications

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“…Treatment of imine 1a with stoichiometric (based on metal) [Cp*RhCl 2 ] 2 and NaOAc cleanly afforded rhodacycle 8 (Scheme a) in nearly quantitative yield. Single crystals of 8 were characterized by X-ray analysis and provided the first structure of a complex obtained by Rh(III)-imidoyl activation …”

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confidence: 99%

Rhodium(III)-Catalyzed Imidoyl C–H Activation for Annulations to Azolopyrimidines

et al. 2018

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Azolopyrimidines are efficiently prepared by direct imidoyl C-H bond activation. Annulations of N-azolo imines with sulfoxonium ylides and diazoketones under redox-neutral conditions and alkynes under oxidizing conditions provide products with various arrangements of nitrogen atoms and carbon substituents. We have also probed the mechanism of this first example of Rh(III)-catalyzed direct imidoyl C-H activation by structural characterization of a catalytically competent rhodacycle obtained after C-H activation and by kinetic isotope effects.

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confidence: 99%

Rhodium(III)-Catalyzed Imidoyl C–H Activation for Annulations to Azolopyrimidines

et al. 2018

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“…377 Upon addition of acetophenone, a Schiff'base reaction and C aryl -H bond activation ensue, thus forming a C,N-rhodacycle.…”

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confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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“…The mechanism proposed for the formation of 4 could not be verified to the extent that the mechanism for the formation of 3a was established, since intermediates in the formation of 4 from 2c and XylNC could not be identified. However, the proposed intermediates and reaction steps of Scheme are supported by well-established chemistry (e.g., migratory insertion involving isoyanides) and by experimental observation of similar intermediates and reaction steps identified in the formation of 3a . Other mechanisms might be possible for the formation of 4 ; for example, the mechanism might involve attack of isocyanide onto the carbene carbon of 2c to facilitate C–C bond formation .…”

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confidence: 66%

Significant Cooperativity Between Ruthenium and Silicon in Catalytic Transformations of an Isocyanide

2016

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Complexes [PhBP3]RuH(η3-H2SiRR′) (RR′ = Me,Ph, 1a; RR′ = Ph2, 1b; RR′ = Et2, 1c) react with XylNC to form carbene complexes [PhBP3]Ru(H)[C(H)(N(Xyl)(η2-H–SiRR′))] (2a–c; previously reported for 2a,b). Reactions of 1a–c with XylNC were further investigated to assess how metal complexes with multiple M–H–Si bonds can mediate transformations of unsaturated substrates. Complex 2a eliminates an N-methylsilacycloindoline product (3a) that results from hydrosilylation, hydrogenation, and benzylic C–H activation of XylNC. Turnover was achieved in a pseudocatalytic manner by careful control of the reaction conditions. Complex 1c mediates a catalytic isocyanide reductive coupling to furnish an alkene product (4) in a transformation that has precedent only in stoichiometric processes. The formations of 3a and 4 were investigated with deuterium labeling experiments, KIE and other kinetic studies, and by examining the reactivity of XylNC with an η3-H2SiMeMes complex (1d) to form a C–H activated complex (6). Complex 6 serves as a model for an intermediate in the formation of 3a, and NMR investigations at −30 °C reveal that 6 forms via a carbene complex (1d) that isomerizes to aminomethyl complex 7d. These investigations reveal that the formations of 3a and 4 involve multiple 4-, 5-, and 6-coordinate silicon species with 0, 1, 2, or 3 Ru–H–Si bonds. These mechanisms demonstrate exceptionally intricate roles for silicon in transition-metal-catalyzed reactions with a silane reagent.

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On the Reactivity Toward Ketones of New Methyl Amino Complexes of Rh(III) and Ag(I). Synthesis of Ortho-Rhodiated Acetophenone Methyl Imine Complexes

Cited by 12 publications

References 25 publications

Rhodium(III)-Catalyzed Imidoyl C–H Activation for Annulations to Azolopyrimidines

Rhodium(III)-Catalyzed Imidoyl C–H Activation for Annulations to Azolopyrimidines

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Significant Cooperativity Between Ruthenium and Silicon in Catalytic Transformations of an Isocyanide

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