艾伦
不对称诱导
钋
级联
部分
手性(物理)
质子化
级联反应
立体专一性
动力学分辨率
重排
氧化膦
重排反应
组合化学
化学
磷化氢
立体化学
有机化学
Nambu–Jona Lasinio模型
离子
对映选择合成
对称性破坏
催化作用
物理
量子力学
手征对称破缺
色谱法
作者
Jia‐Yan Zheng,Handong Wang,Yan Zhang,Zheng Zhang,Jianhua Wu,Xiaoyu Ren,Zhishan Su,Wenchuan Chen,Tianli Wang
标识
DOI:10.1002/anie.202403707
摘要
Despite the significance of chiral allene skeletons in catalysis, organic synthesis and medicinal chemistry et al., there is a scarcity of reports on axially chiral allenyl phosphorus compounds. Here, we disclosed an efficient and straightforward cascade reaction between ethynyl ketones and phosphine oxides, resulting in a broad array of trisubstituted allenes incorporating a phosphorus moiety in high yields with excellent stereoselectivities facilitated by peptide-mimic phosphonium salt (PPS) catalysis, Additionally, comprehensive series of mechanistic experiments have been conducted to elucidate that this cascade reaction proceeds via an asymmetric Pudovik addition reaction followed by a subsequent phospha-Brook rearrangement that occurs concomitantly with kinetic resolution, representing a stereospecific rearrangement and protonation process facilitating central-to-axial chirality transfer in a cascade manner. We anticipate that our research will pave the way for a promising exploration of novel stereo-induction pattern in the Pudovik addition/phospha-Brook rearrangement cascade reaction.
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