Saá / Varela
Research themes
Cyclizations and heterocyclizations catalyzed by transition metals
Main researcher(s)
Group members
| Lago Lorenzo, Laura |
PhD Candidate |
|
| Suárez Lustres, Alejandro |
PhD Candidate |
Research
Organometallic Catalysis: Discovery of New Reactivity and Synthetic Applications
Organic molecules that have great importance and are essential for the welfare of mankind such as active pharmaceutical ingredients, hydrocarbons derived from the chemical industry, new materials, etc, urgently require a more sustainable preparation (high atom economy, no waste generation, etc.). Catalysis is a key technology for the future of sustainability, among which stands out organometallic catalysis. Our research lines are devoted to the discovery of new reactivity through organometallic catalysis and its application in sustainable synthesis of organic molecules, in particular, those that are bioactive (natural and synthetic) and those with emerging electronic properties (new organic materials).
The current research lines are the following:
Catalytic formation of amide/peptide bonds
A wide range of primary and secondary amides can be efficiently synthesized by Ru-catalyzed oxidative amidation of terminal alkynes with primary and secondary amines. The reaction proceeds in chlorinated as well as aqueous medium, with interesting applications in peptide chemistry. The intramolecular variant allows the access to bioactive medium-sized lactams.
Org. Lett. 2019, 21, 5346−5350 Synthesis 2020, 52, 2639-2649
Bioactive five-and six-membered oxa- , aza- and oxaza- heterocycles
2-Vinyl dihydropyrans, 1,3-benzoxazines, vinyl epoxypyrrolidines and benzofused six-membered azaheterocycles have been efficiently synthesized by Ru-catalyzed heterocyclizations of alkyn(ones)als, ortho-(alkynyloxy)benzylamines, aza-alkynals and o-alkynylanilines with diazo compounds.
Angew. Chem. Int. Ed. 2014, 53, 5959-5963 ACS Catalysis 2015, 5, 6255-6262 Angew. Chem. Int. Ed. 2015, 54, 2724-2728 ACS Catalysis 2017, 7, 992-996 Org. Lett. 2020, 22, 2621–2625 Chem. Eur.J. 2020, 26, 7470 –7478 Synlett 2020, 31, 1147-1157
Bioactive seven-membered azaheterocycles and N-doped PAHs
TM-catalyzed oxidative [5+2] annulations of guanidines or triflamides with alkynes or 1,3-dienes have been developed: i) Rh(III) complexes efficiently catalyze the annulation of indolylguanidines with alkynes to 1,3-benzodiazepines (pentacyclic guanidines) using simply O2 as oxidant; ii) Pd(II) complexes efficiently catalyze the annulation of phenethyltriflamides with 1,3-dienes to 3-benzazepines using Cu(OAc)2/O2 as oxidant in a chemo-, regio- and diastereoselective manner and with good to excellent yields.
Org. Lett. 2019, 21, 1779-1783 Org. Lett. 2020, 22, 3591−3595 Adv. Synth. Catal. 2020, 362, 4861-4875
N-doped PAHs (Polycyclic Aromatic Hydrocarbons) have been synthesized by a double Rh(III)-catalyzed [4+2] oxidative cycloaddition of 2-arylbenzimidazoles with alkynes. The new N-doped benzo[c,d]fluoranthenium skeleton possesses intense fluorescence, indicating promising applications as optoelectronic materials.