Resolution of benzylcyclohexylphenylphosphine by palladium(II)-amine metallacycles.: A new ligand for asymmetric hydrovinylation

Resolution of benzylcyclohexylphenylphosphine by palladium(II)-amine metallacycles.: A new ligand for asymmetric hydrovinylation
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DOI:
10.1021/om990302d
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发表时间:
1999-08-16
期刊:
影响因子:
2.8
通讯作者:
Valerga, P
Valerga, P
中科院分区:
化学2区
文献类型:
--
作者:
Albert, J;Cadena, JM;Valerga, P

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本文报道了苄基环己基苯基膦的合成及其在光学活性钯金属配合物中的拆分。用X射线单晶衍射法测定了(R-C,S-P)-[PdCl(C_6H_4CHMeNMe_2)(PB_zCyPh)]的绝对构型。由[Pd(eta(3)-2-MeC 3 H4)Cl(PBzCyPh)]和AgBF 4在CH 2Cl 2溶液中原位合成的烯丙基配合物[Pd(eta(3)-2-MeC 3 H4)(PBzCyPh)S] BF 4,用作苯乙烯和2-乙烯基萘不对称加氢乙烯化反应的预催化剂。该系统允许在非常温和的温度条件(15 ℃)下合成具有良好ee值的3-苯基-1-丁烯和3-(2-萘基)-1-丁烯。
The synthesis of benzylcyclohexylphenylphosphine and its resolution by means of optically active palladium metallacycles are reported. The absolute configuration of (R-C,S-P)-[PdCl(C6H4CHMeNMe2)(PBzCyPh)] has been determined by single-crystal X-ray analyses. The allyl complex [Pd(eta(3)-2-MeC3H4)(PBzCyPh)S]BF4, prepared in situ from [Pd(eta(3)-2-MeC3H4)Cl(PBzCyPh)] and AgBF4 in CH2Cl2 solution, was used as a precatalyst for asymmetric hydrovinylatiom of styrene and 2-vinylnaphthalene. This system permits the synthesis of 3-phenyl-1-butene and 3-(2-naphthyl)-1-butene with good ee values working in very mild conditions of temperature (15 degrees C).