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https://www.ias.ac.in/article/fulltext/jcsc/132/0097

Dynamic domino mechanisms; nonaqueous strongly basic medium; substituted heterocyclic; cascade-like pattern; disproportionation paths; base-catalyzed halogen dance.

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 bromobridged 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

NADER SAKHAEE^{1 2} SAHAR SAKHAEE³ AKBAR MOBARAKI⁴ AHMAD TAKALLOU⁵ MOHAMMAD HOSSEIN SAKHAEE⁶

1. Department of Mathematics and Natural Sciences, Harris-Stowe State University, St. Louis, MO 63108, USA
2. Department of Chemistry, Southern Illinois University Edwardsville, Edwardsville, IL 62025, USA
3. Islamic Azad University, Mashhad Branch, Mashhad, Iran
4. Department of Chemistry, Tarbiat Modarres University, P.O. Box. 14115-175, Tehran, Iran
5. Department of Chemistry, Kharazmi University, Tehran, Iran
6. Mashhad University of Medical Sciences, Mashhad, Iran

Published

7 August 2020

Manuscript received

30 December 2019

Manuscript revised

8 January 2020

Accepted

3 March 2020