Lewis acid catalysis and ligand exchange in the asymmetric binaphthol-catalyzed propargylation of ketones.
1,1'-Bi-2-naphthol (BINOL)-derived catalysts catalyze the asymmetric propargylation of ketones. Density functional theory (DFT) calculations show that the reaction proceeds via a closed six-membered transition structure (TS) in which the chiral catalyst undergoes an exchange process with the original cyclic boronate ligand. This leads to a Lewis acid type activation mode, not a Brønsted acid process, which accurately predicts the stereochemical outcome observed experimentally.
Unilever Centre for Molecular Science Informatics, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Matthew N
MN
Grayson
Jonathan M
JM
Goodman
D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009284:Naphthols / Q000737:chemistry*; D020005:Propanols / Q000138:chemical synthesis* / Q000737:chemistry
D000480:Alkynes; D007659:Ketones; D058116:Lewis Acids; D008024:Ligands; D009284:Naphthols; D020005:Propanols; C028255:propargyl alcohol