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Experimental evidence for the involvement of dinuclear alkynylcopper(I) complexes in alkyne-azide chemistry

机译:双核炔铜(I)配合物参与炔-叠氮化物化学反应的实验证据

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摘要

Dinuclear alkynylcopper(I) ladderane complexes are prepared by a robust and simple protocol involving the reduction of Cu_2(OH)_3OAc or Cu-(OAc)_2 by easily oxidised alcohols in the presence of terminal alkynes; they function as efficient catalysts in coppercatalysed alkyne-azide cycloaddition reactions as predicted by the Ahlquist-Fokin calculations. The same copper(I) catalysts are formed during reactions by using the Sharpless-Fokin protocol. The experimental results also provide evidence that sodium ascorbate functions as a base to deprotonate terminal alkynes and additionally give a con- vincing alternative explanation for the fact that the Cu~I-catalysed reactions of certain 1,3-diazides with phenylacetylene give bis(triazoles) as the major products. The same dinuclear alkynylcopper(I) complexes also function as catalysts in cycloaddition reactions of azides with 1-iodoalkynes.
机译:双核炔基铜(I)梯烷络合物是通过稳健而简单的方法制备的,该方法包括在末端炔烃存在下通过易氧化的醇还原Cu_2(OH)_3OAc或Cu-(OAc)_2。正如Ahlquist-Fokin计算所预测的那样,它们在铜催化的炔-叠氮化物环加成反应中充当有效的催化剂。通过使用Sharpless-Fokin协议在反应过程中形成了相同的铜(I)催化剂。实验结果也提供了证据,表明抗坏血酸钠起着使末端炔烃去质子化的作用,并且还为以下事实提供了令人信服的替代解释:Cu〜I催化某些1,3-叠氮化物与苯乙炔反应生成双(三唑) )作为主要产品。相同的双核炔铜(I)配合物在叠氮化物与1-碘炔烃的环加成反应中也起催化剂的作用。

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