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- W2769656573 endingPage "17944" @default.
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- W2769656573 abstract "2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a highly effective reagent for promoting C–H bond functionalization. The oxidative cleavage of benzylic and allylic C–H bonds using DDQ can be coupled with an intra- or intermolecular nucleophilic addition to generate new carbon–carbon or carbon–heteroatom bonds in a wide range of substrates. The factors that control the reactivity of these reactions are well-defined experimentally, but the mechanistic details and the role of substituents in promoting the transformations have not been firmly established. Herein, we report a detailed computational study on the mechanism and substituent effects for DDQ-mediated oxidative C–H cleavage reactions in a variety of substrates. DFT calculations show that these reactions proceed through a hydride transfer within a charge transfer complex. Reactivity is dictated by the stability of the carbocation intermediate, the degree of charge transfer in the transition states, and, in certain cases, secondary orbital interactions between the π orbital of the forming cation and the LUMO of DDQ. A linear free energy relationship was established to offer a predictive model for reactivity of different types of C–H bonds based on the electronic properties of the substrate." @default.
- W2769656573 created "2017-12-04" @default.
- W2769656573 creator A5021833788 @default.
- W2769656573 creator A5058509481 @default.
- W2769656573 creator A5059016210 @default.
- W2769656573 date "2017-11-30" @default.
- W2769656573 modified "2023-10-18" @default.
- W2769656573 title "Predictive Model for Oxidative C–H Bond Functionalization Reactivity with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone" @default.
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- W2769656573 doi "https://doi.org/10.1021/jacs.7b08902" @default.
- W2769656573 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/29136464" @default.
- W2769656573 hasPublicationYear "2017" @default.
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