Denton Elliott H, Schmitt Hendrik L, Stepanović Olivera, Müller Patrick, Müller Alexander F, Svoboda Daniel, Morandi Bill
Laboratorium für Organische Chemie, ETH Zürich, 8093 Zürich, Switzerland.
J Am Chem Soc. 2025 Jul 23;147(29):25215-25223. doi: 10.1021/jacs.5c01707. Epub 2025 Jul 14.
Herein, we demonstrate that ligand design enables the direct addition of acid chlorides across alkynes in a single step with complete atom economy to afford α,β-unsaturated acid chloride products. This carbochlorocarbonylation reaction, which proceeds through the formal cleavage and reassembly of C-COCl bonds, was developed and explored for a range of acid chlorides and alkynes. During the course of this work, the formation of synthetically useful cyclopentenones through a formal C-H functionalization step was serendipitously observed at elevated temperatures. After optimizing for this divergent reactivity, we explored the substrate scope and undertook experiments to investigate the underlying mechanistic pathway for the formation of this product. Overall, this work expands the carbochlorocarbonylation reaction from activated substrates to alkynes. Further, it provides insight into ligand design for the exploration of fundamental reactivity.
在此，我们证明配体设计能够使酰氯与炔烃一步直接加成，具有完全的原子经济性，从而得到α,β-不饱和酰氯产物。这种碳氯羰基化反应通过C-COCl键的形式断裂和重新组装进行，已针对一系列酰氯和炔烃进行了开发和探索。在这项工作过程中，在高温下意外地观察到通过形式上的C-H官能化步骤形成了具有合成用途的环戊烯酮。在优化这种不同的反应性之后，我们探索了底物范围，并进行了实验以研究该产物形成的潜在机理途径。总体而言，这项工作将碳氯羰基化反应从活性底物扩展到了炔烃。此外，它为探索基本反应性的配体设计提供了见解。
