Controlling first-row catalysts: amination of aryl and heteroaryl chlorides and bromides with primary aliphatic amines catalyzed by a BINAP-ligated single-component Ni(0) complex.
Controlling first-row catalysts: amination of aryl and heteroaryl chlorides and bromides with primary aliphatic amines catalyzed by a BINAP-ligated single-component Ni(0) complex.
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DOI：
10.1021/ja411911s
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发表时间：
2014-01-29
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Ge S;Green RA;Hartwig JF
第一行金属配合物在催化循环的双电子步骤中经常经历不期望的单电子氧化还原过程。我们报道了由明确的单组分镍前体 (BINAP)Ni(η2-NC-Ph)（BINAP = 2,2′-双（联苯膦）-1,1′-联萘）催化的芳基氯化物和芳基溴化物与脂肪族伯胺的胺化反应，最大限度地减少了 Ni(I) 物质和 (BINAP)2Ni 的形成。该反应的范围包括电子变化的芳基氯和含氮杂芳基氯，包括吡啶、喹啉和异喹啉衍生物。机理研究支持镍催化胺化涉及 Ni(0)/Ni(II) 对的催化循环，但与 Ni(I) 卤化物中间体不一致。通过 31P NMR 光谱监测反应混合物，确定 (BINAP)Ni(η2-NC-Ph) 是芳基氯和溴化物胺化过程中催化剂的静止状态。动力学研究表明，芳基氯和芳基溴化物的胺化反应在催化剂和芳基卤中均为一级胺化，在碱和胺中为零级胺化。代表性芳基氯在PhCN中的反应是逆一级反应，但代表性芳基溴在PhCN中是零级反应。 PhCN 中反应顺序的这种差异表明芳基氯与 (BINAP)Ni(0) 反应，后者是由 (BINAP)Ni(η2-NC-Ph) 解离 PhCN 形成的，但芳基溴直接与 (BINAP)Ni(η2-NC-Ph) 反应。总体动力学行为与芳基卤化物与 Ni(0) 的转换限制氧化加成一致。确定了催化剂分解的几种途径，例如催化惰性双（胺）连接的芳基镍（II）氯化物（BINAP）2Ni（0）和Ni（I）物质[（BINAP）Ni（μ-Cl）] 2 的形成。通过使用明确的镍配合物作为催化剂，可以避免 (BINAP)2Ni(0) 的形成，并最大限度地减少 Ni(I) 物质 [(BINAP)Ni(μ-Cl)]2 的形成。
First-row metal complexes often undergo undesirable one-electron redox processes during two-electron steps of catalytic cycles. We report the amination of aryl chlorides and bromides with primary aliphatic amines catalyzed by a well-defined, single-component nickel precursor (BINAP)Ni(η2-NC-Ph) (BINAP = 2,2′-bis(biphenylphosphino)-1,1′-binaphthalene) that minimizes the formation of Ni(I) species and (BINAP)2Ni. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine, quinoline, and isoquinoline derivatives. Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides and bromides is first order in both catalyst and aryl halide and zero order in base and amine. The reaction of a representative aryl chloride is inverse first order in PhCN, but the reaction of a representative aryl bromide is zero order in PhCN. This difference in the order of the reaction in PhCN indicates that the aryl chloride reacts with (BINAP)Ni(0), formed by dissociation PhCN from (BINAP)Ni(η2-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η2-NC-Ph). The overall kinetic behavior is consistent with turnover-limiting oxidative addition of the aryl halide to Ni(0). Several pathways for catalyst decomposition were identified, such as the formation of the catalytically inactive bis(amine)-ligated arylnickel(II) chloride, (BINAP)2Ni(0), and the Ni(I) species [(BINAP)Ni(μ-Cl)]2. By using a well-defined nickel complex as catalyst, the formation of (BINAP)2Ni(0) is avoided and the formation of the Ni(I) species [(BINAP)Ni(μ-Cl)]2 is minimized.
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