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The University of Southampton

Research project: Rios: Asymmetric Organocatalytic methodologies

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Organocatalysis is commonly accepted as the use of small organic molecules to catalyze organic transformations. The term “organocatalysis” was coined by David W. C. MacMillan at the beginning of the 21st century, and was the starting line for breathtaking progress in this area over the last decade. During these last years, this area has grown into one of the three pillars of asymmetric catalysis, complementing and sometimes improving bio- and metal catalysis. The rapid growth in this area can be easily explained: the field offers several advantages to researchers in academia and industry, such as easy and low cost reactions, and reactions that are insensitive to air or moisture (unlike organometallic chemistry). Furthermore, the small chiral organic molecules used as catalysts can be often be derived from nature; thus, they are accessible and inexpensive to prepare, and often, the processes are environmentally friendly. Moreover, the need in industrial large-scale production for removal of impurities related to toxic metal catalysts from the waste stream, which has a huge financial impact, could be avoided with the use of organocatalysts and this has made the field very interesting from the industrial point of view.

The renaissance of organocatalysis was at the beginning of the 21st century, but the origins of small organic molecules acting as catalysts can be traced back to the earliest works of Emil Knoevenagel. In these works, Knoevenagel studied the use of primary and secondary amines, as well as their salts as catalysts for the aldol condensation of β-ketoesters or malonates with aldehydes or ketones. Knoevenagel also suggested the same intermediates that Westheimer later proposed in his retro-aldolization studies. Another key development in the history of organocatalysis was the work of Dakin in 1910 regarding the catalytic activity of primary amino acids in the Knoevenagel reaction. Twenty years later, secondary amines were found by Kuhn and Hoffer that catalyzed not only the Knoevenagel reaction but also the aldol reactions between aldehydes.

Our research group has been devoted to the development of new asymmetric methodologies for the synthesis of enantiopure compounds based in organocatalysis. We focus our interest in the synthesis of interesting targets like quaternary amino acids by organocatalyzed addition of azlactones to vinylsulfones,1 or in a general context the study of the oxazolone reactivity.2

Chemistry formula
Click on image to enlarge

A different area of interest was the development of new methodologies based in the Michael addition to enals catalyzed by secondary amines. For example we developed a methylation of enals using methylenbissulfones as a nucleophile.3

Chemistry formula
click on image to enlarge

Recently, we focus our attention in the development of new organocatalytic methodologies for the synthesis of chiral BODIPYS. Those excellent fluorescents could be used as enantioselective probes in a variety of experiments with biological and chemical interest. The results will be reported soon.

Chemistry formula
click on image to enlarge

Related Publications:

  1. “Enantioselective Organocatalytic Addition of Oxazolones to 1,1-Bis(phenylsulfonyl)ethylene: A Convenient Asymmetric Synthesis of Quaternary alpha-Amino Acids”. A.-N. R. Alba, X. Companyó, G. Valero, A. Moyano, R. Rios. Chem. Eur. J. 2010, 16, 5354-5361
  2. "Enantioselective organocatalytic addition of azlactones to maleimides: A highly stereocontrolled entry to 2,2-disubstituted-2H-oxazol-5-ones" A.-N. R. Alba, G. Valero, T. Calvet, M. Font-Bardia, A. Moyano, R. Rios. Chem. Eur. J. 2010, 16, 9884-9889.
  3. “Formal highly enantioselective organocatalytic addition of alkyl anions to a,ß-unsaturated aldehydes. Aplication to the synthesis of isotope-enantiomers”. A.-N. Alba, X. Companyó, A. Moyano, R. Rios. Chem. Eur. J. 2009, 15, 11095-11099.

Related research groups

Organic Chemistry: Synthesis, Catalysis and Flow
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