Compared with chiral β³-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining chiral β²-amino phosphorus derivatives remains a challenge. These derivatives, which cannot be derived from chiral natural amino acids, possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of chiral β²-amino phosphorus derivatives from E-β-enamido phosphorus compounds is reported by using a green and low-cost earth-abundant metal nickel catalyst (13 examples of 99% ee). In particular, this catalytic system provides the same enantiomer product from the E- and Z-alkene substrates, and the E/Z-substrate mixtures provide good results (up to 96% ee). The products can be diversely derivatized, and the derivatives exhibit good catalytic activities as novel chiral β²-aminophosphine ligands. Density functional theory calculations reveal that the weak attractive interactions between the nickel catalyst and the substrate are crucial for achieving perfect enantioselectivities. In addition, the different coordination modes between the E- or Z-substrates and the catalyst may result in the formation of the same enantiomer product.

中文翻译：

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通过镍催化的不对称氢化合成手性 β2-氨基磷衍生物的对映体选择性合成


与可以很容易地从天然光学纯 α-氨基酸衍生物衍生的手性 β³-氨基磷化合物相比，获得手性β²-氨基磷衍生物仍然是一个挑战。这些衍生物不能来源于手性天然氨基酸，具有独特的生物活性或潜在的催化活性。本文报道了通过使用绿色且低成本的地球丰富的金属镍催化剂（13 个 99% ee 的例子）从 E-β-烯酰胺基磷化合物制备手性β²-氨基磷衍生物的高对映选择性氢化。特别是，该催化系统提供来自 E 和 Z-烯烃底物的相同对映异构体产物，并且 E/Z 底物混合物提供良好的结果（高达 96% ee）。产物可以进行多种衍生化，衍生物作为新型手性β²-氨基膦配体表现出良好的催化活性。密度泛函理论计算表明，镍催化剂和衬底之间的弱吸引力相互作用对于实现完美的对映选择性至关重要。此外，E 或 Z 底物与催化剂之间的不同配位模式可能导致形成相同的对映异构体产物。