Basuri Pallab, Mukhopadhyay Sinchan, Reddy K S S V Prasad, Unni Keerthana, Spoorthi B K, Shantha Kumar Jenifer, Yamijala Sharma S R K C, Pradeep Thalappil
DST Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras, 600036, Chennai, Tamil Nadu, India.
Department of Chemistry, Indian Institute of Technology Madras, 600036, Chennai, Tamil Nadu, India.
Angew Chem Int Ed Engl. 2024 Jul 1;63(27):e202403229. doi: 10.1002/anie.202403229. Epub 2024 May 29.
We present a catalyst-free route for the reduction of carbon dioxide integrated with the formation of a carbon-carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α-carbon of a ketone followed by nucleophilic addition to CO. Online mass spectrometry reveals that the product is an α-ketoacid. Several factors, such as the concentration of the reagents, pressure of CO gas, and distance traveled by the droplets, control the kinetics of the reaction. Theoretical calculations suggest that water in the microdroplets facilitates this unusual chemistry. Furthermore, such a microdroplet strategy has been extended to seven different ketones. This work demonstrates a green pathway for the reduction of CO to useful carboxylated organic products.
我们展示了一种无催化剂的途径，用于在带负电荷的水性微滴的空气/水界面处，于环境温度下将二氧化碳还原，并同时形成碳-碳键。反应通过在酮的α-碳上生成碳负离子，随后亲核加成到CO上进行。在线质谱分析表明产物是α-酮酸。诸如试剂浓度、CO气体压力以及微滴移动距离等几个因素控制着反应动力学。理论计算表明微滴中的水促进了这种不同寻常的化学反应。此外，这种微滴策略已扩展到七种不同的酮。这项工作展示了一条将CO还原为有用的羧化有机产物的绿色途径。
