title: Asymmetric synthesis of functionalized 1,3-diphosphines via chiral palladium complex promoted hydrophosphination of activated olefins.
abstract: Aldehyde, ester- and keto-functionalized monophosphine palladium complexes containing the ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary and reaction promoter were synthesized via hydrophosphination of acrolein and the subsequent Wittig reactions in a one-pot process. Under very mild conditions, the second-stage hydrophosphination of the monophosphine substrates gave the corresponding ester-, keto-, and hydroxyl-functionalized chiral 1,3-bis(diphenylphosphino)propane palladium complexes with good yields and stereoselectivities. The coordination properties and absolute configurations of the novel 1,3-diphosphine complexes were established by single crystal X-ray crystallography. The enantiomerically pure functionalized diphosphine ligands with ester and keto functionalities could be subsequently liberated stereospecifically by treatment of the corresponding dichloro palladium complexes with aqueous potassium cyanide in high yields.
authors.affiliation: Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
authors.forename: Mingjun
authors.initials: M
authors.lastname: Yuan
authors.forename: Na
authors.initials: N
authors.lastname: Zhang
authors.forename: Sumod A
authors.initials: SA
authors.lastname: Pullarkat
authors.forename: Yongxin
authors.initials: Y
authors.lastname: Li
authors.forename: Fengli
authors.initials: F
authors.lastname: Liu
authors.forename: Phuong-Tu
authors.initials: PT
authors.lastname: Pham
authors.forename: Pak-Hing
authors.initials: PH
authors.lastname: Leung
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D009942:Organometallic Compounds; D010720:Phosphines; D010165:Palladium