title: Asymmetric Morita-Baylis-Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back-Reaction Screening.
abstract: An efficient protocol for the evaluation of catalysts for the asymmetric Morita-Baylis-Hillman (MBH) reaction was developed. By mass spectrometric back-reaction screening of quasi-enantiomeric MBH products, an efficient bifunctional phosphine catalyst was identified that outperforms literature-known catalysts in the MBH reaction of methyl acrylate with aldehydes. The close match between the selectivities measured for the forward and back reaction and kinetic measurements provided strong evidence that the aldol step and not the subsequent proton transfer is rate- and enantioselectivity-determining.
authors: Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.
authors: Patrick G
authors: PG
authors: Isenegger
authors: Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.
authors: Florian
authors: F
authors: Bächle
authors: Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.
authors: Andreas
authors: http://orcid.org/0000-0001-9524-2034
authors: A
authors: Pfaltz
keywords: Morita-Baylis-Hillman; asymmetric catalysis; high-throughput screening; mass spectrometry; organocatalysis