Department of Organic Chemistry, University of Regensburg, Universitaetsstrasse 31, 93053, Regensburg, Germany.
Department of Organic Chemistry, University of Tuebingen, Auf der Morgenstelle 18, 72076, Tuebingen, Germany.
Chemistry. 2018 May 17;24(28):7092-7107. doi: 10.1002/chem.201705025. Epub 2018 Feb 5.
While thioesters are common intermediates in biochemical processes, they are much less appreciated in organic synthesis, also compared to other carboxylic acid derivatives. However, their chemistry and reactivity is intriguing and diversified, reaching much further than the acyl substitution and aldol chemistry. Herein, we focus on metal-catalyzed reactions for the synthesis of thioesters as well as their transformations. Reactions such as thiocarbonylation, cross-coupling, decarbonylation, allylic substitution or dual photoredox/metal catalysis are discussed. On one hand, new atom economic methods allow for convenient synthesis of thioesters from well available starting materials. On the other hand, various synthetically important compounds can by synthesized due to the multifaceted reactivity of thioesters that we aimed to depict.
虽然硫酯是生化过程中的常见中间体，但与其他羧酸衍生物相比，它们在有机合成中的应用要少得多。然而，它们的化学性质和反应性非常有趣且多样化，远远超出了酰基取代和醛醇缩合反应。本文重点讨论了用于合成硫酯及其转化的金属催化反应。讨论了诸如硫代羰基化、交叉偶联、脱羰、烯丙基取代或双重光氧化还原/金属催化等反应。一方面，新的原子经济性方法允许从易得的起始原料方便地合成硫酯。另一方面，由于硫酯的多方面反应性，各种具有合成重要性的化合物都可以被合成，这也是我们旨在描绘的内容。
