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P ‐Stereogenic Ferrocene‐Based (Trifluoromethyl)phosphanes: Synthesis, Structure, Coordination Properties and Catalysis
Author(s) -
Sondenecker Aline,
Cvengroš Ján,
Aardoom Raphael,
Togni Antonio
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201001162
Subject(s) - stereocenter , chemistry , trifluoromethyl , dimethylamine , chirality (physics) , catalysis , stereochemistry , enantioselective synthesis , denticity , amine gas treating , ferrocene , stereoselectivity , medicinal chemistry , brønsted–lowry acid–base theory , crystal structure , organic chemistry , electrode , alkyl , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model , electrochemistry
Diastereoselective ortho ‐hydroxymethylation of ( R )‐(1‐ferrocenylethyl)dimethylamine and Brønsted‐acid‐mediatednucleophilic substitution with phenyl(trifluoromethyl)phosphane affords an epimeric mixture of P ‐stereogenic amine–phosphanes 4a and 4b , which are readily separated by crystallization from methanol. Subsequent substitution of the dimethylamino group with diphenylphosphane occurs without epimerization, yielding novel bis(phosphanes) 1a and 1b . These bis(phosphanes) combine three elements of chirality ( C ‐central, P ‐central and planar) and bear a trifluoromethyl group at a stereogenic phosphorus atom. Their complexes with transition metals (Pd, Rh, Ir) were studied and characterized by means of NMR techniques and X‐ray crystallographic analyses, and the bidentate ligands proved efficient in stereoselective catalysis.