Radboud University, Nijmegen, The Netherlands.
Wageningen University and Research Centre, Wageningen, The Netherlands.
Top Curr Chem (Cham). 2016 Apr;374(2):16. doi: 10.1007/s41061-016-0016-4. Epub 2016 Mar 22.
A nearly forgotten reaction discovered more than 60 years ago-the cycloaddition of a cyclic alkyne and an organic azide, leading to an aromatic triazole-enjoys a remarkable popularity. Originally discovered out of pure chemical curiosity, and dusted off early this century as an efficient and clean bioconjugation tool, the usefulness of cyclooctyne-azide cycloaddition is now adopted in a wide range of fields of chemical science and beyond. Its ease of operation, broad solvent compatibility, 100 % atom efficiency, and the high stability of the resulting triazole product, just to name a few aspects, have catapulted this so-called strain-promoted azide-alkyne cycloaddition (SPAAC) right into the top-shelf of the toolbox of chemical biologists, material scientists, biotechnologists, medicinal chemists, and more. In this chapter, a brief historic overview of cycloalkynes is provided first, along with the main synthetic strategies to prepare cycloalkynes and their chemical reactivities. Core aspects of the strain-promoted reaction of cycloalkynes with azides are covered, as well as tools to achieve further reaction acceleration by means of modulation of cycloalkyne structure, nature of azide, and choice of solvent.
一种几乎被遗忘的反应——环状炔烃和有机叠氮化物的环加成反应，生成芳香三唑——已经非常流行。最初是出于纯粹的化学好奇心而被发现，本世纪初又作为一种高效、清洁的生物偶联工具重新被发现，环辛炔-叠氮化物环加成的用途现在已经在化学科学及其他领域得到广泛应用。其操作简单、溶剂相容性广、100%原子效率以及生成的三唑产物的高稳定性，仅举几例，使得这种所谓的应变促进的叠氮-炔环加成反应（SPAAC）成为了化学生物学家、材料科学家、生物技术专家、药物化学家等的首选工具之一。在本章中，首先简要回顾了环炔烃的历史，以及制备环炔烃的主要合成策略及其化学反应性。还介绍了应变促进的环炔烃与叠氮化物反应的核心方面，以及通过调节环炔烃结构、叠氮化物的性质和选择溶剂来实现进一步反应加速的工具。
