[3]Ferrocenophane Ligands with an Inserted Methylene Group

• Published in: European Journal of Organic Chemistry Vol. 2008; no. 30; pp. 5157 - 5161
• Main Authors: Sebesta, Radovan, Bilcik, Filip, Horvath, Branislav
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.10.2008; WILEY‐VCH Verlag; Wiley
• Subjects: Allylic substitution; Asymmetric catalysis; Chemistry; Chemistry, Organic; Ferrocene; Palladium; Phosphane li­gands; Physical Sciences; Science & Technology; ENANTIOPURE; CATALYSIS; MOLECULAR-STRUCTURE; COMPLEXES; ALLYLIC ALKYLATION; Palladium; Asymmetric catalysis; Ferrocene; P,N LIGANDS; DIPHOSPHINE LIGANDS; AMINATION; Allylic substitution; Phosphane ligands; BITE ANGLE; CHIRAL FERROCENE LIGANDS
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200800566

New planar chiral [3]ferrocenophane aminosulfane and aminophosphane ligands displayed interesting results in model Pd‐catalyzed allylic substitution reactions. The phosphane derivative having a methylene group between the cyclopentadienyl ring and the phosphane group showed enantioselectivities up to 86 % ee, whereas the ligand without the methylene group afforded almost racemic allylation products. Analogous sulfane ligands showed the opposite trend. Tentative catalytic complexes were studied by 31P NMR spectroscopy and DFT computational methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) New [3]ferrocenophane ligands with a methylene group inserted between the Cp ring and the donor atom were prepared and evaluated in allylic alkylation reactions. The Pd complex with aminophosphane ligands was found to be an efficient catalyst (up to 86 % ee) for this reaction, whereas the corresponding aminosulfane derivative was inactive.