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Yanli Liu - One of the best experts on this subject based on the ideXlab platform.

Bingchuan Yang - One of the best experts on this subject based on the ideXlab platform.

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Tabitha E. Wood - One of the best experts on this subject based on the ideXlab platform.

  • The Truce-Smiles Rearrangement and Related Reactions: A Review
    Canadian Journal of Chemistry, 2017
    Co-Authors: Anna R.p. Henderson, Joel R. Kosowan, Tabitha E. Wood
    Abstract:

    The Truce–Smiles Rearrangement is an X → C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce–Smiles Rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

  • Truce–Smiles Rearrangement of substituted phenyl ethers
    Organic & biomolecular chemistry, 2015
    Co-Authors: Joel R. Kosowan, Zemane W'giorgis, Ravneet Grewal, Tabitha E. Wood
    Abstract:

    The requirement of aryl ring activation by strong-electron withdrawing substituents in substrates for the intramolecular nucleophilic aromatic substitution reaction known as the Truce–Smiles Rearrangement was examined. Preliminary mechanistic experiments support the SNAr mechanism, including 1H and 13C NMR spectra of a Meisenheimer intermediate formed in situ. The Rearrangement was generally observed to be successful for substrates with strong electron withdrawing substituents, such as nitro-, cyano-, and benzoyl- functional groups, but also for those with multiple, weakly electron withdrawing substituents, such as chloro- and bromo-functional groups. These results lend further clarification to the effect of aryl substituents in this type of SNAr reaction. Additionally, the survey revealed several tandem cyclization and/or elimination reactions accessed by certain substrates.

  • truce Smiles Rearrangement of substituted phenyl ethers
    Organic and Biomolecular Chemistry, 2015
    Co-Authors: Joel R. Kosowan, Ravneet Grewal, Zemane Wgiorgis, Tabitha E. Wood
    Abstract:

    The requirement of aryl ring activation by strong-electron withdrawing substituents in substrates for the intramolecular nucleophilic aromatic substitution reaction known as the Truce–Smiles Rearrangement was examined. Preliminary mechanistic experiments support the SNAr mechanism, including 1H and 13C NMR spectra of a Meisenheimer intermediate formed in situ. The Rearrangement was generally observed to be successful for substrates with strong electron withdrawing substituents, such as nitro-, cyano-, and benzoyl- functional groups, but also for those with multiple, weakly electron withdrawing substituents, such as chloro- and bromo-functional groups. These results lend further clarification to the effect of aryl substituents in this type of SNAr reaction. Additionally, the survey revealed several tandem cyclization and/or elimination reactions accessed by certain substrates.