Chiral Tertiary Amine/L‐Proline Cocatalyzed Enantioselective Morita–Baylis–Hillman (MBH) Reaction

Four types of chiral amines have been synthesized starting from readily available chiral sources. These chiral amines in combination with L-proline have been found to be efficient cocatalysts for the asymmetric Morita–Baylis–Hillman (MBH) reaction between methyl vinyl ketone (MVK) and aromatic aldehydes. The corresponding adducts were formed in reasonable chemical yields and with good enantioselectivities (up to 83 % ee). Moreover, parallel cocatalytic reactions with the two enantiomers of chiral amine 4 and L-proline revealed that it is the proline stereochemistry that determines the configuration of the newly formed chiral center. In addition, the existence of the free hydroxy group in amine 4a enhanced the enantioselectivity of the reaction. Based on these findings, a plausible mechanism for this cocatalytic MBH reaction has been proposed.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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