Research

Organometallic Catalysis and Synthesis

Many organic molecules are of great importance for the human mankind (pharmaceuticals, chemical industry derivatives, new materials, etc.) and thus, the search for efficient syntheses of organic compounds must be of great interest. In this respect, the catalysis is a key technology for the future. Our research is dedicated to the elaboration and application of new catalytic methods in organic chemistry in order to facilitate new and better synthetic ways to organic molecules, specifically, in the synthesis of natural and synthetic bioactive products and in new organic materials.
The present research interests are outlined as follow:

1. Metal-catalyzed C-H activation

1.1 Insertion into Csp3-H bonds by metal carbenes

New synthetic routes to functionalized bicyclic and spirane structures were optimized using new tandem reactions via in situ generated catalytic ruthenium-carbenes followed by Csp3-H bond insertion in alkynyl acetals, ethers and amines.
 
Angew. Chem. Int. Ed. 2012, 51, 723-727
 

1.2 Csp2- and Csp3-H bond activation in nitrogen derivatives: synthesis of bioactive heterocycles

Bioactive 2-methylindol skeletons can be afforded through a rhodium-catalyzed tandem allylation of a Csp2-H bond with allylic carbonates followed by an oxidative cyclization of o-allylanilides.
 
Org. Lett. 2013, 15, 4576-4579

2. Metal-catalyzed cyclizations

2.1 [2+2+2] and [4+2+2] cycloadditions of pi systems

Ruthenium-catalyzed reactions of alkenes (cyclic or acyclic) and 1,3-dienes to 1,6-diynes easily afford functionalized bicyclic 1,3-cyclohexadienes and 1,3,5-cyclooctatrienes via [2+2+2] and [4+2+2] cycloadditions.


Org. Lett. 2003, 5, 2841-2844
J. Am. Chem. Soc. 2006, 128, 9262-9263
Org. Lett. 2009, 11, 983-986
 

2.2 Carbo- and heterocyclizations

Functionalized cyclopentenes and cyclohexenes can be easily prepared by new Ru-catalyzed cyclization reactions of terminal alkynals and 1,6-diynes.

 

J. Am. Chem. Soc. 2006, 128, 9576-9577
J. Am. Chem. Soc. 2007, 129, 12916-12917
 
Heterocyclic units present in many bioactive compounds such as benzofurans, isochromenes, benzoxepines and dihydroisoquinolines can be easily synthesized by ruthenium- and osmium-catalyzed cycloisomerizations of aromatic alkynols and alkynamides. The key step is the nucleophilic attack of the heteroatom to the catalytic metal-vinylidene species generated in situ.

 

Org. Lett. 2009, 11, 5350-5353
Angew. Chem. Int. Ed. 2010, 49, 4278-4281
Adv. Synth. Catal. 2011, 353, 1933-1937
 

2.3 Brønsted acid-catalyzed carbocyclizations

Linear enyne acetals were efficiently converted into hydroazulene skeletons (found in many bioactive terpene derivatives) by a new Brønsted acid-catalyzed tandem reaction of carbocyclization/Nazarov cyclization. The process takes place in a stereospecific manner.

 

Org. Lett. 2009, 11, 1531-1533
Angew. Chem. Int. Ed. 2012, 51, 12316-12320