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Special Issue "Baylis-Hillman Reaction and Related Processes"

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (31 January 2010)

Special Issue Editor

Special Issue Information

Published Papers (3 papers)

Gianluca Martelli, Eleonora Marcucci, Mario Orena and Samuele Rinaldi Communication: Enantiopure Derivatives of Aza-Baylis-Hillman Adducts by Subsequent SN′-SN′ Reactions of Acylcarbamates Bearing a Chiral Auxiliary Molecules 2009, 14(8), 2824-2835; doi:10.3390/molecules14082824 Received: 7 July 2009; in revised form: 22 July 2009 / Accepted: 30 July 2009 / Published: 30 July 2009 Show/Hide Abstract | Download PDF Full-text (257 KB) Abstract: Reactions of(4S,5R)-1-(3,4-Dimethyl-2-oxo-5-phenylimidazolidine)carbonyl-isocyanate (4) with appropriate Baylis-Hillman adducts 5 gave the corresponding acyl carbamates 6,7 as equimolar diastereomeric mixtures. These mixtures were treated with DABCO, to afford with moderate diastereoselection easily separable [2-(3",4"-dimethyl-2"-oxo-5"-phenylimidazolidine-1-carboxamido)(aryl)methyl]acrylates 8 and 9.

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Verónica Carrasco-Sanchez, Mario J. Simirgiotis and Leonardo S. Santos Review: The Morita-Baylis-Hillman Reaction: Insights into Asymmetry and Reaction Mechanisms by Electrospray Ionization Mass Spectrometry Molecules 2009, 14(10), 3989-4021; doi:10.3390/molecules14103989 Received: 24 August 2009; in revised form: 1 October 2009 / Accepted: 10 October 2009 / Published: 12 October 2009 Show/Hide Abstract | Download PDF Full-text (737 KB) Abstract: This short review presents new insights on the mechanism and online monitoring using electrospray ionization tandem mass spectrometry (ESI–MS/MS) of Morita–Baylis–Hillman (MBH) reactions. MBH reactions are versatile carbon-carbon organocatalyzed bond forming reactions, making them environmentally friendly due to general organocatalysts employed. The organocatalyst behavior, which controls the transition state and thus the enantioselectivities in the obtained products, is very important in the performance of asymmetric MBH transformations. Some recent techniques and advances in asymmetric transformations are reviwed, as well as online reaction monitoring and analysis of the reaction intermediates. The mechanism accepted nowadays is also review through the insights gained from the use of ESI–MS/MS techniques.

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Javier Mansilla and José M. Saá Review: Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues Molecules 2010, 15(2), 709-734; doi:10.3390/molecules15020709 Received: 19 January 2010; in revised form: 25 January 2010 / Accepted: 29 January 2010 / Published: 1 February 2010 Show/Hide Abstract | Download PDF Full-text (797 KB) 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.

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Last update: 25 September 2009