Synthesis, characterization, and catalytic application of a new chiral P,N-indene ligand derived from ( R)-BINOL

• Published in: Journal of organometallic chemistry Vol. 694; no. 12; pp. 1943 - 1947
• Main Authors: Wechsler, Dominik, Schatte, Gabriele, Stradiotto, Mark
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 15.05.2009; Elsevier
• Subjects: Asymmetric catalysis; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Chiral; Indene; P,N-ligand; Physical Sciences; Rhodium; Science & Technology; Indene; Rhodium; P,N-ligand; Asymmetric catalysis; Chiral; ENANTIOSELECTIVE HYDROSILYLATION; COMPLEXES; QUINOLINES; P,N-SUBSTITUTED INDENE; P,N LIGANDS; P,N-LIGANDS; NITROGEN; ASYMMETRIC HYDROGENATION; CONJUGATE ADDITION; RHODIUM(I)
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2009.02.015

We report the synthesis and characterization of a new chiral P,N-indene ligand, our efforts to develop the rhodium coordination chemistry of this ligand, and the application of this ligand in rhodium-mediated asymmetric alkene hydrogenation and ketone hydrosilylation. Lithiation of 2-dimethylaminoindene followed by quenching with [( R)-(1,1′-binaphthalene-2,2′-diyl)]chlorophosphite and treatment with triethylamine afforded the crystallographically characterized enantiopure P,N-indene 3 in 71% isolated yield. In the course of rhodium coordination chemistry studies involving 3, the formation of the isolable complex [(κ 2- P, N- 3)(κ 1- P,N- 3)RhCl] ( 7) (81%) was observed, thereby confirming the propensity of this new ligand to form L n Rh( 3) 2 complexes. Such coordination chemistry behavior may contribute in part to the generally poor catalytic performance exhibited by mixtures of 3 and rhodium precursor complexes in the asymmetric hydrogenation and hydrosilylation studies described herein.