Carbazo-anilines: Enantioselective cross-dehydrogenative amination reactions for the preparation of unsymmetrical chiral diamines molecules, and their applications as enantiopure ligands
Final Report Abstract
In conclusion, the project was in large part devoted to the exploration of the redox reactivity of phenothiazines (PTZs) and derivatives, in particular in metal-free cross dehydrogenative coupling reactions with phenols and indoles. Indeed, a notable serendipitous discovery at the beginning of project, led us to explore this reactivity. Although we deviated considerably from our original project objectives, we are nevertheless now closer to reaching the main objective than before (enantioselective C-N bond forming coupling reactions with H-bonded axial chirality). Indeed, many of the herein coupling methods operate now at more moderate temperatures, some at only 40 °C, and the vast majority of the new C-N coupled products are C-N chiral in the case of unsymmetrically substituted phenothiazine starting materials. Indeed, in most cases, a strong intramolecular O-H•••N Hydrogen-bond is evidenced by IR and X-ray. These objectives remain therefore on our list of realistic future goals.
Publications
- O2-mediated dehydrogenative amination of phenols. Angew. Chem. Int. Ed. 2015, 54, 4102
M.-L. Louillat-Habermeyer, R. Jin & F. W. Patureau
(See online at https://doi.org/10.1002/anie.201500089) - Mild, periodate mediated, dehydrogenative C-N bond formation with phenothiazines and phenols, Org. Lett. 2016, 18, 4491
R. Jin, F. W. Patureau
(See online at https://doi.org/10.1021/acs.orglett.6b02223) - The cumene/O2 system: a very simple tool for the radical chain oxidation of some functional groups. N. J. Chem. 2017, 41, 6981
A. Malekafzali, K. Malinovska, F. W. Patureau
(See online at https://doi.org/10.1039/c7nj01666b) - Mechanism of the Dehydrogenative Phenothiazination of Phenols. Chem. Eur. J. 2018, 24
M. Goswami, A. Konkel, M. Rahimi, M.-L. Louillat-Habermeyer, H. Kelm, R. Jin, B. de Bruin, F. W. Patureau
(See online at https://doi.org/10.1002/chem.201800730) - Phenothiazinimides: atom-efficient electrophilic amination reagents. Org. Lett., 2018, 20, 2884
R. Jin, C. L. Bub, F. W. Patureau
(See online at https://doi.org/10.1021/acs.orglett.8b00914) - The strong Beta-CF3 shielding effect in HFIP and 100 other organic solvents revisited with O NMR. ChemCatChem 2018, 10, 1547
A. Bernhardt, H. Kelm, F. W. Patureau
(See online at https://doi.org/10.1002/cctc.201701721)
