Department Chemie, Johannes Gutenberg University, Duesbergweg 10-14, 55128, Mainz, Germany.
Chem Rec. 2021 Sep;21(9):2344-2353. doi: 10.1002/tcr.202100078. Epub 2021 May 6.
The morphinans are an important class of structurally fascinating and physiologically important natural products as exemplified by the famous opium alkaloids of the morphine family. Although this class of secondary metabolites from the juice of the opium poppy capsule was already used for medicinal purposes thousands of years ago, chemical modifications are still being applied to the core structure today in order to achieve the most specific effect on the various receptor subtypes possible with the fewest possible side effects. The unusual architecture of the morphinan core has also proven to be a highly challenging target for total synthesis. This review highlights electrosynthetic approaches towards natural and semisynthetic morphinan alkaloids. The historical progress in applying anodic aryl-aryl couplings to the construction of the morphinan framework is described in chronological order while particular benefits and challenges concerning the electrochemical transformations are grouped together, including the influence of substitution patterns, protecting groups, and reaction conditions.
吗啡烷类是一类结构引人入胜且生理作用重要的天然产物，以著名的吗啡类鸦片生物碱为代表。尽管几千年前罂粟汁中的这类次级代谢产物已被用于医疗用途，但为了尽可能减少副作用而对各种受体亚型产生最特异的效果，对其核心结构的化学修饰仍在不断进行。吗啡烷核心的这种特殊结构也被证明是全合成的极具挑战性的目标。本文综述了电化学方法在天然和半合成吗啡烷生物碱中的应用。本文按时间顺序描述了阳极芳基-芳基偶联在吗啡烷骨架构建中的历史进展，同时将电化学转化的特殊益处和挑战分组在一起，包括取代模式、保护基和反应条件的影响。
