Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic gem -Dichlorides.
Martín Piñeiro-SuárezAndrés M Álvarez-ConstantinoMartín Fañanás-MastralPublished in: ACS catalysis (2023)
A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem -dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem -dichloride and provides chiral internal 1,5-dienes featuring ( Z )-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the ( Z )-alkenyl chloride.
Keyphrases
- density functional theory
- ionic liquid
- room temperature
- molecular dynamics
- photodynamic therapy
- electron transfer
- crystal structure
- genome wide
- molecular dynamics simulations
- cancer therapy
- dna methylation
- single cell
- monte carlo
- gene expression
- squamous cell carcinoma
- amino acid
- capillary electrophoresis
- solid state
- mass spectrometry