Molecules 2010, 15(2), 709-734; doi:10.3390/molecules15020709
Review

Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues

Received: 19 January 2010; in revised form: 25 January 2010 / Accepted: 29 January 2010 / Published: 1 February 2010
(This article belongs to the Special Issue Baylis-Hillman Reaction and Related Processes)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract: Conscious of the importance that stereochemical issues may have on the design of efficient organocatalyts for both Morita-Baylis-Hillman and aza-Morita-Baylis-Hillman reaction we have analyzed them in this minireview. The so-called standard reactions involve “naked” enolates which therefore should lead to the syn adducts as the major products, irrespective of the E, Z stereochemistry of the enolate. Accordingly, provided the second step is rate determining step, the design of successful bifunctional or polyfunctional catalysts has to consider the geometrical requirements imposed by the transition structures of the second step of these reactions. On the other hand, MBH and aza-MBH reactions co-catalyzed by (S)-proline and a secondary or tertiary amine (co-catalyst) involve the aldol-type condensation of either a 3-amino-substituted enamine, dienamine, or both, depending on the cases. A Zimmerman-Traxler mechanism defines the stereochemical issues regarding these co-catalyzed condensations which parallel those of the well established (S)-proline catalyzed aldol-like reactions.
Keywords: Morita-Baylis-Hillman reaction; aza-Morita-Baylis-Hillman reaction; stereochemistry; bifunctional catalysts; polyfunctional catalysts; (S)-proline-amine co-catalysis
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MDPI and ACS Style

Mansilla, J.; Saá, J.M. Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues. Molecules 2010, 15, 709-734.

AMA Style

Mansilla J, Saá JM. Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues. Molecules. 2010; 15(2):709-734.

Chicago/Turabian Style

Mansilla, Javier; Saá, José M. 2010. "Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues." Molecules 15, no. 2: 709-734.

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