Rowett Albert C, Sweeting Stephen G, Heard David M, Lennox Alastair J J
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
Angew Chem Int Ed Engl. 2024 May 21;63(21):e202400570. doi: 10.1002/anie.202400570. Epub 2024 Apr 18.
The haloform reaction from methyl ketones to carboxylic acids is one of the oldest known synthetic organic reactions, which has been used in myriad applications over the decades. The corresponding reaction to produce esters is, however, less developed, as the reaction is generally limited to simple, primary alcohols that are used in solvent-level quantities, thereby restricting the complexity of esters that can be directly formed. Herein, we detail the development of a general ester-forming haloform coupling reaction using one equivalent of alcohol. Mechanistic and kinetic modelling studies demonstrated that the key intermediates are formed under equilibrium, which facilitated the development of conditions that are amenable to secondary alcohols.
从甲基酮到羧酸的卤仿反应是已知最古老的有机合成反应之一，几十年来已被广泛应用。然而，相应的生成酯的反应发展较少，因为该反应通常仅限于使用溶剂级用量的简单伯醇，从而限制了可直接形成的酯的复杂性。在此，我们详细介绍了一种使用一当量醇的通用酯形成卤仿偶联反应的开发。机理和动力学建模研究表明，关键中间体是在平衡条件下形成的，这有助于开发适用于仲醇的反应条件。
