手性膦配体/催化剂——SadPhos 108将
基于非C2对称性、刚柔并济和兼具软硬配位原子(O, S, N, P原子)的设计理念，开发了12个系列含有手性叔丁基亚磺酰胺膦配体/催化剂（Sulfinamide Phosphine，统称：SadPhos）。其兼具有结构多样，便于修饰，易于克级制备等众多优点。SadPhos在过渡金属的不对称催化和有机小分子催化中都表现出了优异的催化性能和对映选择性。本次推介“108将”涵盖了Ming-Phos、Xu-Phos、PC-Phos、Xiao-Phos、Wei-Phos、Xiang-Phos、TY-Phos、Peng-Phos等。
在过渡金属催化的反应中，Ming-Phos、Xu-Phos、PC-Phos、Xiao-Phos、Wei-Phos、Xiang-Phos、TY-Phos等作为单膦配体、P, N-配体、P, S-配体、P, O-配体，可与金、铜、钯、铱、镍、铑、银、钴等8种过渡金属采用自适应性的配位模式，展现出了非常优异的催化效率及不对称诱导能力。目前，其已高效应用于Suzuki偶联、烯烃的双氨化、亚磷酸酯芳基化、氢芳化反应、不对称氢化、Heck/醚化反应、烯烃的碳硼化、插羰反应、烯烃芳基/炔基化、C-S 交叉偶联、C-H芳基化、联烯γ-加成、烯烃还原Heck、烯烃的碳碘化、光催化偶联、卡宾芳硅化、联烯C-P偶联、炔烃的氢膦化、烯烃双芳基、烯烃的碳氧化、联烯硼/羰基化、Heck/Tsuji-Trost反应、环加成反应、聚合反应等。
在有机小分子催化的反应中，Xiao-Phos、Wei-Phos、Peng-Phos等通过亚磺酰胺提供氢给体，是一类非常高效的多功能手性叔膦催化剂。其已成功地应用于不对称分子内和分子间的Rauhut-Currier 反应、缺电子亚胺与联烯酸酯的γ-加成反应、烯酮或联烯酮参与的不对称 [4+2] 环加成反应、a, β-不饱和酮与TMSN3的双官能团化反应、3-硝基吲哚与联烯酸酯的去芳构化[3+2]环加成反应和不对称烯丙基化等反应中，并取得了优异的反应结果。
参考文献
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