A new P,S-Chiral auxiliary derived from thioglucose. X-ray structure of a palladium 1,3-diphenylallyl complex with a strongly rotated allyl ligand
A new P,S-Chiral auxiliary derived from thioglucose. X-ray structure of a palladium 1,3-diphenylallyl complex with a strongly rotated allyl ligand
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DOI：
10.1021/om950983m
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发表时间：
1996-05-14
期刊：
影响因子：
2.8
通讯作者：
Wick, K
中科院分区：
文献类型：
--
作者：
Albinati, A;Pregosin, PS;Wick, K
以硫代葡萄糖为原料，合成了一种新的二茂铁基P，S-手性助剂1，并将其用于钯催化的不对称烯丙基烷基化反应。烯丙基阳离子配合物[Pd（eta（3）-PhCHCHPh）（1）] CF_3SO_3（2）的X-射线结构显示了一个明显旋转的1，3-二苯基烯丙基配体，使得末端烯丙基碳C（3），反式到磷给体，约为1，3-二苯基烯丙基。0.85（3）低于协调平面的埃。这种畸变与在烯丙基烷基化反应中预期的Pd（0）过渡态络合物有关。
The new ferrocene-based P,S-chiral auxiliary 1, derived from thioglucose, has been prepared and used in the palladium-catalyzed enantioselective allylic alkylation reaction. The X-ray structure of the allyl cationic complex [Pd(eta(3)-PhCHCHCHPh)(1)]CF3SO3 (2) reveals a markedly rotated 1,3-diphenylallyl ligand such that the terminal allyl carbon C(3), trans to the phosphorus donor, is ca. 0.85(3) Angstrom below the coordination plane. This distortion is pertinent to the Pd(0) transition state complex expected in the allylic alkylation reaction.