四川大学王天利团队报道了制备手性三取代烯Pudovik加成/Phospha-Brook重排的新型立体感应模式。相关研究成果发表在2024年3月23日出版的《德国应用化学》。

尽管手性烯骨架在催化、有机合成和药物化学等方面具有重要意义，但关于轴向手性烯丙基磷化合物的报道却很少。

该文中，研究人员公开了乙炔基酮和氧化膦之间有效而直接的级联反应，在肽模拟鏻盐（PPS）催化的促进下，以高产率和优异的立体选择性产生了广泛的包含磷部分的三取代烯。

此外，研究人员进行了一系列全面的机理实验来阐明，这种级联反应是通过不对称的Pudovik加成反应进行的，随后是伴随动力学分辨率发生的磷-布鲁克重排，这代表了一种立体特异性重排和质子化过程，以级联方式促进中心到轴向的手性转移。该研究将为在Pudovik加成/磷-布鲁克重排级联反应中，探索一种新的立体诱导模式铺平道路。

附：英文原文

Title: Novel Stereo-Induction Pattern in Pudovik Addition/Phospha-Brook Rearrangement towards Chiral Trisubstituted Allenes

Author: Jia-Yan Zheng, Fan Wang, Yan Zhang, Zheng Zheng, Jia-Hong Wu, Xiaoyu Ren, Zhishan Su, Wenchuan Chen, Tianli Wang

Issue&Volume: 2024-03-23

Abstract: 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, a 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 a novel stereo-induction pattern in the Pudovik addition/phospha-Brook rearrangement cascade reaction.

DOI: 10.1002/anie.202403707

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202403707