Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory

Autor: Patureau, F.W., Siegler, M.A.M., Spek, A.L., Sandee, A. J., Jugé, S., Aziz, S., Berkessel, A., Reek, J.N.H., Rontgen participation programme, Sub Crystal and Structural Chemistry
Přispěvatelé: Homogeneous and Supramolecular Catalysis (HIMS, FNWI)
Jazyk: angličtina
Rok vydání: 2012
Předmět:
Zdroj: European Journal of Inorganic Chemistry, 2012(3), 496. Wiley-VCH Verlag
European Journal of Inorganic Chemistry, 2012(3), 496-503. Wiley-VCH Verlag
ISSN: 1434-1948
DOI: 10.1002/ejic.201100811
Popis: 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.
Databáze: OpenAIRE
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