Tailored ligand acceleration of the Cu-catalyzed azide-alkyne cycloaddition reaction: practical and mechanistic implications.
Tailored ligand acceleration of the Cu-catalyzed azide-alkyne cycloaddition reaction: practical and mechanistic implications.
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DOI：
10.1021/ja105743g
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发表时间：
2010-10-20
影响因子：
15
通讯作者：
Finn MG
中科院分区：
文献类型：
--
作者：
Presolski SI;Hong V;Cho SH;Finn MG
制备了含有1,2,3-三唑基、2-苯并咪唑基和2-吡啶基组分混合物的三（杂环甲基）胺，用于铜催化叠氮-炔环加成反应的配体加速。确定了两类配体：一类在配位溶剂中产生高反应速率，但与铜相比，过量使用时会抑制反应过程，另一类在水中提供快速催化作用，过量使用则不会抑制反应。几种“混合”配体在两种条件下都表现良好。动力学测量作为配体：金属比和催化剂浓度的函数被发现与活性Cu2L配方一致。由于强结合的螯合剂并不总是最有效的，因此需要对反应混合物中潜在的供体分子进行评估。提供了简单的规则来指导用户选择有效的配体和反应条件，以适应大多数类型的底物，溶剂和浓度。
Tris(heterocyclemethyl)amines containing mixtures of 1,2,3-triazolyl, 2-benzimidazoyl, and 2-pyridyl components were prepared for ligand acceleration of the copper-catalyzed azide-alkyne cycloaddition reaction. Two classes of ligands were identified: those that give rise to high reaction rates in coordinating solvents but which inhibit the process when used in excess relative to copper, and those that provide for fast catalysis in water and are not inhibitory in excess. Several “mixed” ligands were identified that performed well under both types of conditions. Kinetics measurements as a function of ligand:metal ratio and catalyst concentration were found to be consistent with an active Cu2L formulation. Since strongly bound chelating agents are not always the most effective, achieving optimal rates requires an assessment of the potential donor molecules in the reaction mixture. Simple rules are provided to guide the user in the choice of effective ligands and reaction conditions to suit most classes of substrates, solvents, and concentrations.
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影响因子：
15
作者：
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通讯作者：
Gajewski, JJ
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