https://hdl.handle.net/10680/1776 Sun, 26 Feb 2023 23:11:14 GMT 2023-02-26T23:11:14Z https://hdl.handle.net/10680/1780 Truce–Smiles rearrangement of substituted phenyl ethers Kosowan, Joel R.; W’Giorgis, Zemane; Grewal, Ravneet; Wood, Tabitha E. 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. post-print Tue, 26 May 2015 00:00:00 GMT https://hdl.handle.net/10680/1780 2015-05-26T00:00:00Z https://hdl.handle.net/10680/1778 长度的影响范围地理休战后微笑rangement reactions Fuss, David; Wu, Yu Qi; Grossi, Michael R.; Hollett, Joshua W.; Wood, Tabitha E. This report examines the effect of substrate design upon the Truce‐Smiles rearrangement, an intramolecular nucleophilic aromatic substitution reaction. The length of the molecular spacer that tethers the carbanion nucleophile to the substituted benzene ring was found to have a strong influence on the ability of the substrate to undergo the reaction successfully. Our experimental results show highest yield of desired aryl migration product for substrates designed with a 3‐atom tether, which proceed through a 5‐membered spirocyclic intermediate. The results are interpreted in comparison with a survey of Truce‐Smiles rearrangements described in the literature and found to be consistent. Computational studies support the observed reactivity trend and suggest an explanation of a favorable combination of ring strain and electrostatic repulsion leading to optimal reactivity of the substrate designed with a 3‐atom tether. Comparison of our results with trends for related ring‐closing reactions illustrate the unique electrostatic features of the system studied herein. post-print Fri, 07 Jul 2017 00:00:00 GMT https://hdl.handle.net/10680/1778 2017-07-07T00:00:00Z https://hdl.handle.net/10680/1777 The Truce–Smiles rearrangement and related reactions: a review Henderson, Anna R. P.; Kosowan, Joel R.; Wood, Tabitha E. 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. post-print Mon, 16 Jan 2017 00:00:00 GMT https://hdl.handle.net/10680/1777 2017-01-16T00:00:00Z