Investigación

Catálise Organometálica e Síntese

Moitas moléculas orgánicas teñen gran importancia para a humanidade coma os produtos farmacéuticos, os derivados da industria química, os novos materiais, etc. e, por tanto, é moi relevante a preparación eficiente de ditos compostos orgánicos. A este respecto, a catálise é unha tecnoloxía clave de cara ao futuro. As nosas liñas de investigación están adicadas a elaboración e aplicación de novos métodos catalíticos na área da química orgánica co fin de faciclitar novas e mellores rutas de formación de moléculas orgánicas, en particular, na síntese de produtos naturais e sintéticos bioactivos e en novos materiais orgánicos.
As liñas de investigación actuais son as seguintes:

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