6533b826fe1ef96bd1284959
RESEARCH PRODUCT
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
F.w. PatureauM.a.m. SieglerA.l. SpekA. J. SandeeS. JugéS. AzizA. BerkesselJ.n.h. ReekRontgen Participation ProgrammeSub Crystal And Structural Chemistrysubject
Inorganic Chemistrychemistry.chemical_compoundEnantiopure drugchemistryStereochemistryLigandAsymmetric hydrogenationSupramolecular chemistryEnantioselective synthesisProtonationCombinatorial chemistryTautomerProtic solventdescription
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral ligands with up to 99 % ee, and apply them in the Rh-catalyzed asymmetric hydrogenation of alkenes. These ligands are interesting new building blocks in the area of acid/base-type noninnocent ligand catalysis.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2011-09-28 | European Journal of Inorganic Chemistry |