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Transition-Metal-Free Allylic Borylation of 1,3-Dienes.

Ricardo J MazaElliot DavenportNúria MirallesJorge J CarbóElena Fernández
Published in: Organic letters (2019)
This work explains the reactivity of diboron reagents with 1,3-dienes in a transition-metal-free context. The sole addition of Na2CO3 (30 mol %) to bis(pinacolato)diboron in MeOH allows the 1,4-hydroboration of cyclic and noncyclic 1,3-dienes. The electronic influence on the substrate guarantees the conjugated 1,4-hydroboration versus 1,2-diboration. DFT calculations show that the distribution of charge in the allylic anion intermediate governs the selectivity toward 1,4-hydroboration, while the favored trans configuration in diene reagents determines the preference for the E allyl boronate products.
Keyphrases
  • transition metal
  • density functional theory
  • ionic liquid
  • molecular dynamics
  • molecular dynamics simulations
  • photodynamic therapy
  • molecular docking
  • structural basis
  • solar cells
  • crystal structure