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Asymmetric Morita–Baylis–Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back‐Reaction Screening
Author(s) -
Isenegger Patrick G.,
Bächle Florian,
Pfaltz Andreas
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604616
Subject(s) - aldol reaction , bifunctional , chemistry , catalysis , phosphine , baylis–hillman reaction , enantioselective synthesis , enantiomeric excess , organic chemistry , kinetic resolution , acrylate , reaction rate , enantiomer , combinatorial chemistry , polymer , monomer
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.