Palladium-catalyzed coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates: a general method for the preparation of primary arylamines.
Palladium-catalyzed coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates: a general method for the preparation of primary arylamines.
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DOI：
10.1021/ja903049z
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发表时间：
2009-08-12
影响因子：
15
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Vo, Giang D.;Hartwig, John F.
我们报道，由 Pd[P(o-tol)3]2 和烷基双膦 CyPF-t-Bu 生成的络合物是一种高活性和选择性催化剂，用于氨与芳基氯、溴化物、碘化物和磺酸盐的偶联。用氨的二恶烷溶液进行氨与该催化剂的偶联，以高产率从各种芳基亲电子试剂形成伯芳胺。低至 0.1 mol% 的催化剂负载量足以满足许多芳基氯化物和芳基溴化物的反应。在这种催化剂的存在下，芳基磺酸盐也首次与氨发生高产率偶联。该催化剂存在下的反应与现有铜和钯体系存在下的反应的比较揭示了互补的（如果不是更广泛的底物范围）。该方法用于生成酰胺、酰亚胺和氨基甲酸酯的实用性通过由芳基溴和氯化物一锅合成这些羰基化合物的小库来说明。机理研究表明，Pd[P(o-tol)3]2 和 CyPF-t-Bu 生成的催化剂比 CyPF-t-Bu 和钯(II) 前体生成的催化剂更具活性和通用性，因为钯(II)、氨和碱的组合生成的活性催化剂浓度较低。
We report that the complex generated from Pd[P(o-tol)3]2 and the alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates. The couplings of ammonia with this catalyst conducted with a solution of ammonia in dioxane form primary arylamines from a variety of aryl electrophiles in high yields. Catalyst loadings as low as 0.1 mol % were sufficient for reactions of many aryl chlorides and bromides. In the presence of this catalyst, aryl sulfonates also coupled with ammonia for the first time in high yields. A comparison of reactions in the presence of this catalyst versus those in the presence of existing copper and palladium systems revealed a complementary, if not broader substrate scope. The utility of this method to generate amides, imides and carbamates is illustrated by a one-pot synthesis of a small library of these carbonyl compounds from aryl bromides and chlorides. Mechanistic studies show that Pd[P(o-tol)3]2 and CyPF-t-Bu generate a more active and general catalyst than that generated from CyPF-t-Bu and palladiun(II) precursors because of the low concentration of active catalyst that is generated from the combination of palladium(II), ammonia and base.
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