Ph-tetraMe-Bithienine, the First Member of the Class of Chiral Heterophosphepines: Synthesis, Electronic and Steric Properties, Metal Complexes and Catalytic Activity
Articolo
Data di Pubblicazione:
2013
Citazione:
Ph-tetraMe-Bithienine, the First Member of the Class of Chiral Heterophosphepines: Synthesis, Electronic and Steric Properties, Metal Complexes and Catalytic Activity / L. Vaghi, T. Benincori, R. Cirilli, E. Alberico, P.R. Mussini, M. Pierini, T. Pilati, S. Rizzo, F. Sannicolò. - In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1434-193X. - 2013:36(2013), pp. 8174-8184. [10.1002/ejoc.201301098]
Abstract:
Unknown 1H-2,7-dihydro-1-phenylphosphepine, containing
a 2,2 ,5,5 -tetramethyl-3,3 -bithiophene atropisomeric scaffold
(Ph-tetraMe-Bithienine), and its oxide have been synthesized
and structurally characterized by single-crystal Xray
diffraction analysis. The most evident structural feature
is the very small dihedral angle. The electronic properties of
the phosphane were quantitatively evaluated by cyclic voltammetry
and compared with three other 2,7-dihydro-1-
phenylphosphepines differing in the nature of the biaromatic
scaffold (biphenyl, 1,1 -binaphthyl and 2,2 -dimethoxybiphenyl). The racemate of the phosphane oxide was resolved
into antipodes, which were reduced to the enantiopure
phosphanes and employed as ligands in Rh and Pt complexes
in homogeneous stereoselective catalytic reactions. The
enantioselective ability and catalytic activity of the new mediators
were found to be quite modest in the hydrogenation
reactions of olefinic double bonds, whereas good performances
were achieved in specific C–C bond-forming reactions.
The results are interpreted on the basis of the steric and electronic
properties of the ligand.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
L. Vaghi, T. Benincori, R. Cirilli, E. Alberico, P.R. Mussini, M. Pierini, T. Pilati, S. Rizzo, F. Sannicolò
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