55650-55-0Relevant academic research and scientific papers
Planar chiral alkenylferrocene phosphanes: Preparation, structural characterisation and catalytic use in asymmetric allylic alkylation
?těpni?ka, Petr,Lama?, Martin,Císa?ová, Ivana
, p. 446 - 456 (2008/03/18)
Planar chiral alkenylferrocene phosphanes, viz. (Sp)-[Fe(η5-C5H3-1-PPh2-2-CH{double bond, long}CR2)(η5-C5H5)] (R = H, (Sp)-2; Ph, (Sp)-5) and (Sp)-[Fe(η5-C5H3-1-PPh2-2-(E)-CH{double bond, long}CHR)(η5-C5H5)] (R = Ph, (Sp)-3; C(O)CH3, (Sp)-6; and CO2CH2CH3, (Sp)-7) have been prepared by alkenylation of (Sp)-2-(diphenylphosphanyl)ferrocenecarboxaldehyde and tested as ligands for enantioselective palladium-catalysed allylic alkylation of 1,3-diphenyprop-2-en-1-yl acetate with dimethyl malonate. All phosphanylalkenes formed active catalysts. However, the induced enantioselectivity was only poor to moderate [12-43% ee after 20 h at room temperature], with the ee's and configuration of the preferred product strongly depending on the ligand structure. The catalytic results have been related to solution properties (NMR, ESI MS) and the solid-state structural data (X-ray diffraction) of [Pd(η3-1,3-Ph2C3H3){(Sp)-2-η2:κP}]ClO4 ((Sp)-12), which represent a model of the plausible reaction intermediate.
Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphosphine-Transition Metal Complexes. I. Preparation of Chiral Ferrocenylphosphines
Hayashi, Tamio,Mise, Takaya,Fukushima, Motoo,Kagotani, Masahiro,Nagashima, Nobuo,et al.
, p. 1138 - 1151 (2007/10/02)
As chiral ligands for transition metal complex catalyzed asymmetric reactions, various kinds of chiral ferrocenylphosphines, which have planar chirality due to 1,2-unsymmetrically substituted ferrocene structure and also have a functional group on the side chain of the ferrocene nucleus, were prepared. (S)-N,N-dimethyl-1-ethylamine , (S)-N,N-dimethyl-1-ethylamine , and their dimethylphosphino derivatives were prepared by way of lithiation of optically resolved N,N-dimethyl-1-ferrocenylethylamine.The 1-(dimethylamino)ethyl group on the ferrocenylphosphines was converted stereospecifically by nucleophilic substitution reactions into 1-methoxy-, 1-hydroxy-, 1-diphenylphosphino-, and several 1-(dialkylamino)ethyl groups. 1-Diphenylphosphino-2-(dimethylaminomethyl)ferrocene (FcPN) was optically resolved via its phosphine sulfide dibenzoyltartaric acid salt.The relationship between CD spectra of the chiral ferrocenylphosphines and the configuration of their planar chirality is discussed.
