| Title | Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality |
|---|---|
| Authors | CARMONA CARMONA, JOSÉ ALBERTO, Hornillos, Valentin , Ramirez-Lopez, Pedro , Ros, Abel , Iglesias-Siguenza, Javier , Gomez-Bengoa, Enrique , Fernandez, Rosario , Lassaletta, Jose M. |
| External publication | Si |
| Means | J. Am. Chem. Soc. |
| Scope | Article |
| Nature | Científica |
| JCR Quartile | 1 |
| SJR Quartile | 1 |
| JCR Impact | 14.695 |
| Publication date | 05/09/2018 |
| ISI | 000444219100022 |
| DOI | 10.1021/jacs.8b05819 |
| Abstract | A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd-0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd-0/Josiphos ligand] to obtain axially chiral heterobiaryl alpha-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a beta-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction. |
| Universidad Loyola members |