Highly reactive, single-component nickel catalyst precursor for Suzuki-Miyuara cross-coupling of heteroaryl boronic acids with heteroaryl halides.
Highly reactive, single-component nickel catalyst precursor for Suzuki-Miyuara cross-coupling of heteroaryl boronic acids with heteroaryl halides.
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DOI：
10.1002/anie.201207428
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发表时间：
2012-12-14
影响因子：
16.6
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Ge, Shaozhong;Hartwig, John F.
Suzuki-Miyaura （SM）交叉偶联反应是药物化学中最常见的构建C-C键的催化过程，而这些偶联反应在钯催化剂上进行得最多用第一排丰富的金属镍代替贵金属钯用于SM联轴器，可以显著降低催化剂的成本。镍配合物催化的SM偶联，由于镍(0)对氯芳烃的高反应活性，使得一些更具有挑战性的偶联反应可以在含有简单配体的催化剂上发生。在这类交叉偶联反应中已经报道了几种镍催化剂[3]，这些镍催化剂对苯酚衍生物[4]（如磺酸盐、[5]醚、[6]酯、[7]氨基甲酸酯、[8]碳酸酯和氨基甲酸酯）的偶联异常活跃。[8b]然而，现有的用于SM交叉偶联的镍催化剂存在两个普遍的缺点：要实现高产量的偶联需要高催化剂负载（3-10 mol% Ni），而且这些交叉偶联的范围不包括形成杂联芳基产物的反应，而杂联芳基产物对医药和农用化学应用很重要。杂芳基化合物的催化合成具有挑战性，因为杂芳基偶联伙伴的连接可能会毒害催化剂。大多数这种催化杂联芳基合成是通过钯催化的Suzuki-Miyaura或still - migita交叉偶联实现的，钯负载为2-4 mol%镍催化剂也被用来进行这种偶联反应。然而，由镍配合物催化的两种杂芳基试剂之间的偶联范围仅限于2-或3-噻吩基新戊基糖硼酸盐与3-甲磺酸基吡啶或氨基磺酸盐的特定反应。[5d， e]目前还没有报道过镍催化剂能与高周转率反应并偶联两个杂芳基底物。
The Suzuki–Miyaura (SM) cross-coupling reaction is the most frequently conducted catalytic process to construct C–C bonds in medicinal chemistry,[1] and these coupling reactions are conducted most frequently with palladium catalysts.[2] The replacement of the precious metal palladium with the first-row, abundant metal nickel for SM couplings could significantly reduce the cost of the catalyst. SM couplings catalyzed by nickel complexes, because of the high reactivity of nickel (0) toward chloroarenes could allow some of the more challenging coupling reactions to occur with catalysts containing simple ligands. Several nickel catalysts have been reported for this class of cross-coupling reaction,[3] and these nickel catalysts are unusually active for the coupling of phenol derivatives [4] such as sulfonates,[5] ethers,[6] esters,[7] carbamates,[8] carbonates, and sulfamates.[8b] However, there are two general drawbacks to the existing nickel catalysts for SM cross-couplings: high catalyst loading (3–10 mol% Ni) is required to achieve the coupling in high yield, and the scope of these cross-couplings does not encompass reactions that form hetero-biaryl products, which are important for medicinal and agrochemical applications.Catalytic syntheses of the hetero-biaryl compounds are challenging because the ligation of the heteroaryl coupling partner can poison the catalyst. The majority of such catalytic hetero-biaryl syntheses have been achieved by palladium-catalyzed Suzuki–Miyaura or Stille–Migita cross-couplings with a 2–4 mol% palladium loading.[9] Nickel catalysts have also been employed to conduct such coupling reactions. However, the scope of the couplings between two heteroaryl reagents catalyzed by a nickel complex is limited to the specific reactions of 2-or 3-thienyl neopentylglycolboronate with pyrid-3-yl mesylate or sulfamate.[5d, e] No nickel catalyst that reacts with high turnover numbers and couples two heteroaryl substrates has been reported.
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