Dimethyl Diazomalonate

Audia, James E.; Droste, James J.; Gevorgyan, Vladimir; Rubin, Michael; Chan, Wing Chi; Yu, Wing‐Yiu; McLarney, Brett D.; France, Stefan

doi:10.1002/047084289x.rd323.pub4

Cited by 1 publication

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“…To address this limitation while making the proposed model more accessible, we developed another steric parameter, r′ (Figure 13). r′ represents the R−O distance in the anion of the corresponding β-carbonyl ester (6). r′ can be easily calculated using commercial molecular modeling software (e.g., Spartan, Macromodel, etc.).…”

Section: Predictive Modelmentioning

confidence: 99%

“…Therefore, this Article investigates the reactivity of dirhodium(tetracarboxylate)-carbene complexes, derived from A−A diazo compounds, with alkane substrates in an aim to develop generalized predictive rules for their effective utilization in selective intermolecular C(sp 3 )−H functionalization reactions. Previous investigations of intermolecular C(sp 3 )−H functionalization reactions have focused solely on carbenes derived from dimethyl diazomalonate 6 and thus similarly lack comprehensiveness. 22,23 As such, little is known on the influence of the nature of the acceptor groups on A−A carbene C(sp 3 )−H insertion in an intermolecular dirhodium(tetracarboxylate)catalyzed manifold.…”

Section: Introductionmentioning

confidence: 99%

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Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

et al. 2019

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Intermolecular C(sp3)–H insertions of β-carbonyl ester dirhodium-carbenes are extremely rare. Toward developing efficient reactions of these carbenes, a model for their insertion into C(sp3)–H bonds is described using density functional theory (DFT) calculations. In this study, the relevant electronic and steric components of β-carbonyl ester dirhodium-carbenes that affect intermolecular C(sp3)–H activation energies are explored, parametrized, and used to construct an intuitive model for predicting propensity for C–H insertion. The resulting insights from the theoretical investigation are actualized through experiments to establish reactivity trends for these species and reaction discovery. On the basis of these integrated computational and experimental efforts, examples of intermolecular C(sp3)–H insertions featuring secondary α-diazo-β-amide esters are reported. The resulting carbenes feature an intramolecular 1,6-hydrogen bond that affords increased stability and enhanced reactivity for C(sp3)–H insertion as compared to other β-carbonyl ester dirhodium-carbenes. The reactivity of these carbenes is also highlighted through (1) an example of a cyclopropanation reaction and (2) the use of a chiral dirhodium catalyst system.

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Section: Predictive Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

et al. 2019

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Dimethyl Diazomalonate

Cited by 1 publication

References 97 publications

Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

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Dimethyl Diazomalonate

Cited by 1 publication

References 97 publications

Predictive Model for the [Rh2(esp)2]-Catalyzed Intermolecular C(sp3)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

Predictive Model for the [Rh2(esp)2]-Catalyzed Intermolecular C(sp3)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

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Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment

Predictive Model for the [Rh₂(esp)₂]-Catalyzed Intermolecular C(sp³)–H Bond Insertion of β-Carbonyl Ester Carbenes: Interplay between Theory and Experiment