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Inducing high exo selectivity in Diels–Alder reaction by dimethylborane substituent: a DFT study

Taherinia, D ; Sharif University of Technology | 2022

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  1. Type of Document: Article
  2. DOI: 10.1038/s41598-022-26685-y
  3. Publisher: Nature Research , 2022
  4. Abstract:
  5. In this work, the role of Lewis acid–base (LAB) interaction on the stereoselectivity of the Diels–Alder (DA) reaction has been studied by DFT in gas and solution (dichloromethane) phases. The calculations were performed at the B3LYP/6-311G++ (d, p) level. Two different series of DA reactions were investigated: (1)—three mono-substituted cyclopentadienes + dimethyl(vinyl)borane; (2)—five α,β-unsaturated carbonyl compounds + cyclopenta-2,4-dien-1-yldimethylborane. The reacting diene and dienophile pairs were chosen to restrict LAB interaction to the exo reaction pathway. It was found that in some of the examined cases, the favorable LAB interaction is so strong that it can lead to a completely exo-selective DA reaction. Furthermore, a novel multistep synthetic method was hypothesized for preparing exo cycloadduct with near 100% stereoselectivity. Our results can open up new avenues toward the rational design of exo-selective DA reactions for synthesizing novel bioorganic compounds. © 2022, The Author(s)
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  8. Source: Scientific Reports ; Volume 12, Issue 1 , 2022 ; 20452322 (ISSN)
  9. URL: https://www.nature.com/articles/s41598-022-26685-y