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Catalytic access to ferrocenyl phosphines bearing both planar and central chirality – A kinetic resolution approach via catalytic asymmetric P(III)–C bond formation
Tetrahedron ( IF 2.1 ) Pub Date : 2020-05-20 , DOI: 10.1016/j.tet.2020.131259
Abdul Sadeer , Tadayuki Kojima , Jia Sheng Ng , Kennard Gan , Renta Jonathan Chew , Yongxin Li , Sumod A. Pullarkat

A series of enantioenriched ferrocenyl monophosphines imbued with both central and planar chirality were obtained catalytically (80–99% ee) via the kinetic resolution of 1,2-disubstituted planar chiral ferrocenyl enone racemates. The synthetic approach utilized a chiral palladacycle to facilitate the asymmetric hydrophosphination (AHP) as a means to achieve high stereoselectivity. The enantioenriched ferrocenylphosphine products could be protected and further recrystallized to obtain ees up to 99%. The modularity of the phosphine framework obtained was demonstrated via derivatization of its functional handles via a simple nucleophilic substitution to yield optically pure bisphosphines.



中文翻译:

催化接触同时具有平面和中心手性的二茂铁基膦–通过催化不对称P(III)-C键形成的动力学拆分方法

通过1,2-二取代的平面手性二茂铁基烯酮外消旋体的动力学拆分,可催化获得一系列具有中心和平面手性的富烯二茂铁基单膦酸酯(80-99%ee)。合成方法利用手性palladacycle来促进不对称氢磷酸化(AHP),以实现高立体选择性。可以保护富含对映体的二茂铁基膦产品,并进一步重结晶以获得高达99%的ee。通过简单的亲核取代作用衍生出其功能手柄,得到光学上纯的双膦,证明了所获得的膦骨架的模块性。

更新日期:2020-05-20
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