Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
J Am Chem Soc. 2009 Nov 4;131(43):15769-76. doi: 10.1021/ja9054096.
Phototriggering of the metal-free azide to acetylene cycloaddition reaction was achieved by masking the triple bond of dibenzocyclooctynes as cyclopropenone. Such masked cyclooctynes do not react with azides in the dark. Irradiation of cyclopropenones results in the efficient (Phi(355) = 0.33) and clean regeneration of the corresponding dibenzocyclooctynes, which then undergo facile catalyst-free cycloadditions with azides to give corresponding triazoles under ambient conditions. In situ light activation of a cyclopropenone linked to biotin made it possible to label living cells expressing glycoproteins containing N-azidoacetyl-sialic acid. The cyclopropenone-based phototriggered click chemistry offers exciting opportunities to label living organisms in a temporally and spatially controlled manner and may facilitate the preparation of microarrays.
通过将二苯并环辛炔的三键掩蔽为环丙烯酮，实现了无金属叠氮化物到炔烃环加成反应的光触发。这种被掩蔽的环辛炔在黑暗中不会与叠氮化物反应。环丙烯酮的辐照导致相应的二苯并环辛炔的有效（Phi(355) = 0.33）和清洁再生，然后在环境条件下与叠氮化物进行容易的无催化剂环加成，得到相应的三唑。将与生物素连接的环丙烯酮进行原位光活化，使得标记含有 N-叠氮乙酰神经氨酸的糖蛋白的活细胞成为可能。基于环丙烯酮的光触发点击化学为以时间和空间控制的方式标记活生物体提供了令人兴奋的机会，并可能有助于微阵列的制备。
