Wu Xiaoqiang, Lu Shanya, Zhong Wei, Xu Tao
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai, China.
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, China.
Nat Commun. 2025 Apr 16;16(1):3628. doi: 10.1038/s41467-025-58990-1.
Brønsted base-mediated [1,2]-phospha-Brook rearrangements have garnered considerable attention for developing new methodologies and efficiently constructing complex molecular structures. However, the strict reliance on pentavalent phosphonates imposes strong limitations on the reaction types, and the mechanistic constraint also excludes the involvement of trivalent phosphine in the same pathway. In this study, we employ Lewis acid rather than Brønsted base to shift the charge transfer from the previous O-P-C direction to a P-C-O process. This orthogonal approach can undergo the unprecedented C-O bond cleavage instead of traditional C-P bond splitting and enables the deoxygenative phosphorylation of carbonyl compounds under metal-free conditions to rapid access various tertiary phosphine oxides. The reaction demonstrates excellent substrate scope, remarkable functional group compatibility, and operational simplicity, offering significantly enhanced atom-economy compared to previous deoxygenative strategies. Additionally, detailed mechanistic studies reveal an unusual oxygen atom crossover and clearly elucidate the mechanism of this Lewis acid-mediated trivalent phospha-Brook rearrangement. These insights further deepen the understanding of trivalent phosphorus chemistry and pave the way for the design of related reactions.
布朗斯台德碱介导的[1,2]-磷-布鲁克重排反应在开发新方法和高效构建复杂分子结构方面备受关注。然而，对五价膦酸酯的严格依赖对反应类型施加了很大限制，并且其机理限制也排除了三价膦在同一途径中的参与。在本研究中，我们采用路易斯酸而非布朗斯台德碱，将电荷转移方向从之前的O-P-C方向转变为P-C-O过程。这种正交方法能够实现前所未有的C-O键断裂而非传统的C-P键断裂，并能在无金属条件下实现羰基化合物的脱氧磷酸化反应，从而快速获得各种叔膦氧化物。该反应展示了出色的底物范围、显著的官能团兼容性和操作简便性，与之前的脱氧策略相比，原子经济性显著提高。此外，详细的机理研究揭示了一种不寻常的氧原子交叉现象，并清晰地阐明了这种路易斯酸介导的三价磷-布鲁克重排反应的机理。这些见解进一步加深了对三价磷化学的理解，并为相关反应的设计铺平了道路。
