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)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Ⅷ的总收率达19.5%,手性高效液相色谱分析其ee值达95%。
( 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 Ⅲwith n-BuLi and following phosgenation with C1PPh2 provided (R)-N,N-dimethyl-( S)- 1-(2-diphenylphosphinoferrocenyl) ethylamine ( Ⅳ). (R) -1-[ (S) -2-(diphenylphosphino) ferrocenyl 1 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.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2011年第12期1236-1239,共4页
Fine Chemicals
基金
国家科技支撑计划项目(2011BAE06A07)~~