(R)-1-[(S)-2-(二苯基膦)二茂铁基]乙基二(3,5-二甲基苯基)膦的合成

The synthesis of (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]

摘要:

以乙酰基二茂铁为原料，经过钯催化氢化胺化及(R)-(+)-酒石酸拆分制备了 (R)-1-二茂铁基乙基二甲胺(III)；III与正丁基锂作用后，与二苯基氯化膦作用得到N，N-二甲基-(R)- 1-[(S)-2-(二苯基膦基)二茂铁基]乙胺(IV)；IV与新制的二(3，5-二甲基苯基)膦烷发生构型保持的取代反应，得到双膦配体(R)-1-[(S)-2-(二苯基膦)二茂铁基]乙基二(3,5-二甲基苯基)膦 (VIII)。以乙酰基二茂铁计V的总收率达19.5%，手性高效液相分析其ee值达95%。

Abstract:

(R)-1-Ferrocenylethyldimethylamine (III) was synthesized from acetylferrocene via a hydrogenative amination catalyzed with Pd/C and chemical resolution with (R)-(+)-tartaric acid. Lithiation of III with n-BuLi and following phosgenation with ClPPh2 provided (R)-N, N-dimethyl-(S)-1-(2-diphenylphosphinoferrocenyl)ethylamine (IV); (R) -1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosiphine (VIII) was obtained by treatment of IV with freshly prepared di(3,5-dimethylphenyl)phosphine through a configurationally retentive displacement in an overall yield of 19.5% calculated from acetylferrocene, The ee of which was about 95% according to the chiral HPLC analysis.