Synthesis, resolution and reactions of (±)-1-(dimethylarsino)-2-(methylphenylphosphino)benzene. Crystal and molecular structure of [(S), (S)]-(+)<sub>589</sub>-{2-[1-(dimethylamino)ethyl]phenyl-C<sup>1</sup>,N}[1-(dimethylarsino)-2-(methylphenylphosphino)benzene-As,P]palladium(<scp>II</scp>) hexafluorophosphate
作者:Roy J. Doyle、Geoffrey Salem、Anthony C. Willis
DOI:10.1039/dt9950001867
日期:——
absolute configuration of the R enantiomer of the ligand has been assigned by a crystal-structure determination of the least-soluble diastereomeric complex [(S),(S)]-(+)589-2-[1-(dimethylamino)ethyl]phenyl-C1, N}[1-(dimethylarsino)-2-(methylphenylphosphino)benzene-As,P]palladium(II) hexafluorophosphate. Chemoselective cleavage of the dimethylarsino moiety of the free benzene derivative occurs in the
通过使二甲基砷化钠与(±)-1-氯-2-(甲基苯基膦基)苯在四氢呋喃中反应制得不对称的双齿(±)-1-(二甲基砷基)-2-(甲基苯基膦基)苯。它的拆分是通过分步结晶分离一对含有外消旋配体和原金属化的(S)-二甲基(1-苯乙基)胺的内部非对映体钯(II)配合物而实现的。光学纯的对映体具有α±32°(589 nm,二氯甲烷)。配体的R对映异构体的绝对构型已通过最不溶非对映异构体配合物[(S),(S)]-(+)589的晶体结构确定来确定-2- [1-(二甲基氨基)乙基]苯基-C 1,N } [1-(二甲基砷基)-2-(甲基苯基膦基)苯-As ,P ]钯(II)六氟磷酸盐。在四氢呋喃中存在锂金属的情况下,发生游离苯衍生物的二甲基ar基部分的化学选择性裂解。