13119-15-8Relevant articles and documents
Optical resolution and the stereoelectronic properties of chelating (±)-[(methylsulfinyl)methyl]diphenylphosphine
Leung, Pak-Hing,Quek,Lang, Huifang,Liu,Mok,White, Andrew J. P.,Williams, David J.,Rees, Nicholas H.,McFarlane, William
, p. 1639 - 1643 (2007/10/03)
Optical resolution of the asymmetric chelating agent (±)-Ph2PCH2S(O)Me has been achieved via fractional crystallization of a pair of diastereomeric palladium(II) cationic complexes containing the sulfinyl-substituted ligand and ortho-metallated (S)-[1-(dimethylamino)ethyl]naphthalene. The X-ray structural analysis of the perchlorate salt of the less-soluble diastereomer confirmed that the sulfinyl-substituted phosphine co-ordinated to the palladium via phosphorus and oxygen with the non-co-ordinated sulfur having an R absolute configuration. An unusual electronic repulsion is observed between palladium and the non-bonded sulfur lone pair thus directing the methyl substituent on sulfur to a sterically unfavored axial position. Furthermore, a two-dimensional rotating frame Overhauser enhancement 1H NMR study of the complex in CDCl3 confirmed that this intramolecular electronic interaction outweighs the general steric considerations in solution. Optically pure (R)-(+)-Ph2PCH2-S(O)Me was displaced from the resolving palladium complex with 1,2-bis(diphenylphosphino)ethane.
A Horner-Wittig synthesis of 1-chlorovinyl sulfoxides
Otten,Davies,Van Der Gen
, p. 449 - 452 (2007/10/03)
1-Chlorovinyl sulfoxides 1 were prepared by Horner-Wittig reaction of the readily accessible [(α-chloro)sulfinylmethyl)diphenylphosphine oxides 2 with aldehydes. Excellent Z-selectivity was observed in most cases.
