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Mechanistic pathways for halogen dance reactions in bromo-thiophenes: a cascade-like pattern

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Abstract

Ever since the halogen dance reaction was discovered by Bunnet et al, synthetic chemists have utilized the transformation in many desirable ways to build substituted heterocyclic target molecules of all kind. Using DFT-Cam-B3LYP/ land2dz computations and focused on Hannes Frohlich et al. Halogen Dance (HD) reactions of bromothiophenes, a new bromo-bridged Transition State (TS) is proposed. This bromo-bridged TS was then used to put forth eight possible isomerization as well as eight possible disproportionation paths. These mechanistic pathways were then carefully inspected based on TS’s energy and protonation/deprotonation steps to find the most suitable pathways. Collectively these mechanistic pathways joined like a jigsaw puzzle to give, for the first-time, a fully comprehensive cascade-like pattern for base-catalyzed halogen dance in its entirety. The present work may well shed light on a dynamic domino mechanism which dominates the realm of nonaqueous strongly basic medium, organic chemistry, reactions.

Graphic abstract

C-Br reactivity and σ-holes in bromothiophenes are shown to be the major mechanistic driving force in their base catalyzed Halogen dance reactions.

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Supplementary Information (SI)

Figures S1–S2, Z-Matrices and Table S1 are available at www.ias.ac.in/chemsci.

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Authors and Affiliations

  1. Department of Mathematics and Natural Sciences, Harris-Stowe State University, St. Louis, MO, 63108, USA

    NADER SAKHAEE

  2. Department of Chemistry, Southern Illinois University Edwardsville, Edwardsville, IL, 62025, USA

    NADER SAKHAEE

  3. Islamic Azad University, Mashhad Branch, Mashhad, Iran

    SAHAR SAKHAEE

  4. Department of Chemistry, Tarbiat Modarres University, P.O. Box. 14115-175, Tehran, Iran

    AKBAR MOBARAKI

  5. Department of Chemistry, Kharazmi University, Tehran, Iran

    AHMAD TAKALLOU

  6. Mashhad University of Medical Sciences, Mashhad, Iran

    MOHAMMAD HOSSEIN SAKHAEE

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  1. NADER SAKHAEE
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Correspondence to NADER SAKHAEE.

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SAKHAEE, N., SAKHAEE, S., MOBARAKI, A. et al. Mechanistic pathways for halogen dance reactions in bromo-thiophenes: a cascade-like pattern. J Chem Sci 132, 97 (2020). https://doi.org/10.1007/s12039-020-01786-1

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  • DOI: https://doi.org/10.1007/s12039-020-01786-1

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