Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine
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 stru...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
1998
|
| _version_ | 1826305173532704768 |
|---|---|
| author | Leung, P Quek, G Lang, H Liu, A Mok, K White, A Williams, D Rees, N McFarlane, W |
| author_facet | Leung, P Quek, G Lang, H Liu, A Mok, K White, A Williams, D Rees, N McFarlane, W |
| author_sort | Leung, P |
| collection | OXFORD |
| description | 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. |
| first_indexed | 2024-03-07T06:28:52Z |
| format | Journal article |
| id | oxford-uuid:f5442f98-3bb8-4978-8f8d-e38ec4d6bb70 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:28:52Z |
| publishDate | 1998 |
| record_format | dspace |
| spelling | oxford-uuid:f5442f98-3bb8-4978-8f8d-e38ec4d6bb702022-03-27T12:26:05ZOptical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphineJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:f5442f98-3bb8-4978-8f8d-e38ec4d6bb70EnglishSymplectic Elements at Oxford1998Leung, PQuek, GLang, HLiu, AMok, KWhite, AWilliams, DRees, NMcFarlane, WOptical 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. |
| spellingShingle | Leung, P Quek, G Lang, H Liu, A Mok, K White, A Williams, D Rees, N McFarlane, W Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title | Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title_full | Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title_fullStr | Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title_full_unstemmed | Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title_short | Optical resolution and the stereoelectronic properties of chelating (+/-)-[(methylsulfinyl)methyl]diphenylphosphine |
| title_sort | optical resolution and the stereoelectronic properties of chelating methylsulfinyl methyl diphenylphosphine |
| work_keys_str_mv | AT leungp opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT quekg opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT langh opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT liua opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT mokk opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT whitea opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT williamsd opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT reesn opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine AT mcfarlanew opticalresolutionandthestereoelectronicpropertiesofchelatingmethylsulfinylmethyldiphenylphosphine |