Brotherton Wendy S, Michaels Heather A, Simmons J Tyler, Clark Ronald J, Dalal Naresh S, Zhu Lei
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
Org Lett. 2009 Nov 5;11(21):4954-7. doi: 10.1021/ol9021113.
Cu(II) salts accelerate azide-alkyne cycloaddition reactions in alcoholic solvents without reductants such as sodium ascorbate. Spectroscopic observations suggest that Cu(II) undergoes reduction to catalytic Cu(I) species via either alcohol oxidation or alkyne homocoupling, or both, during an induction period. The reactions involving 2-picolylazide are likely facilitated by its chelation to Cu(II). The highly exothermic reaction between 2-picolylazide and propargyl alcohol completes within 1-2 min in the presence of as low as 1 mol % Cu(OAc)(2).
在没有诸如抗坏血酸钠等还原剂的情况下,铜(II)盐可加速醇类溶剂中的叠氮化物-炔烃环加成反应。光谱观测表明,在诱导期内,铜(II)通过醇氧化或炔烃自偶联或两者兼而有之,被还原为催化活性的铜(I)物种。涉及2-吡啶甲基叠氮化物的反应可能因其与铜(II)的螯合作用而得到促进。在低至1 mol%的醋酸铜(II)存在下,2-吡啶甲基叠氮化物与炔丙醇之间的高度放热反应在1-2分钟内即可完成。