Trivalent Phospha-Brook rearrangement enabled practical deoxygenative phosphonylation of carbonyls
Year: 2025
Type: article
Abstract: 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. Although Brønsted base-mediated [1,2]- phospha-Brook rearrangements have garnered considerable attention in the development of new methodologies, the strict reliance on pentavalent phosphonates imposes strong limitations on new reaction types. Here, the authors disclose a Lewis acid-mediated trivalent [1,2]- phospha-Brook rearrangement with carbonyl compounds to rapidly access tertiary phosphine oxides.
Source: Nature Communications
Authors: Xiaoqiang Wu, Shanya Lu, Wei Zhong, Tao XU
Institutions: Tongji University, Jiaxing University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $6,990
OpenAlex ID: W4409493834