Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones |
| |
| Authors: | Zhen He Xiaotian Qi Shiqing Li Yinsong Zhao Prof?Dr Ge Gao Prof?Dr Yu Lan Yiwei Wu Prof?Dr Jingbo Lan Prof?Dr Jingsong You |
| |
| Institution: | 1. Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (P. R. China);2. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (P. R. China) |
| |
| Abstract: | A transition‐metal‐free formal decarboxylative coupling reaction between α‐oxocarboxylates and α‐bromoketones to synthesize 1,3‐diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal‐based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the α‐bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate‐determining step is an unusual hydrogen‐bond‐assisted enolate formation by thermolysis. |
| |
| Keywords: | cross‐coupling decarboxylation enolates homogeneous catalysis synthetic methods |
|
|
