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首页> 外文期刊>Chemistry: A European journal >Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex
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Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex

机译：探索使用低价镍络合物的区域选择性键裂解和交叉偶联反应

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Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}(2)(-(2):(2)-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form (2)-carbonyl complexes. In contrast, acetylthioesters underwent rapid C-acyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an (2)-carbonyl complex, phenyl esters were found to predominantly undergo C-aryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean C-aryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.
机译：近年来，酯作为交叉偶联反应的重金属化伙伴受到了广泛关注。在这里，我们报告了一系列与[{（dtbpe）Ni}（2）（-（2）:( 2）-C6H6）]（dtbpe = 1,2-bis（二叔丁基）膦氨基甲酸乙酯），它是（dtbpe）镍（0）的来源。发现三氟甲基硫代酯形成（2）-羰基配合物。相反，乙酰基硫酯快速进行C-酰基-S键裂解，然后脱羰基生成甲基镍配合物。可以通过添加CO将脱羰基向后推，从而使硫酯再生。发现大多数硫酯配合物与苯基硼酸进行化学计量交叉偶联，生成硫化物。尽管还发现三氟乙酸乙酯形成了（2）-羰基配合物，但发现苯酯主要经历了C-芳基-O键裂解，从而生成了芳基镍配合物。这些也可以进行金属转移以产生联芳基。配体争夺产生双（乙酸）镍配合物阻碍了使反应具有催化性的尝试，其形成受到独立合成的支持。最后，还发现乙酸2-萘酯进行了清洁的C-芳基-O键裂解，尽管与苯基硼酸的化学计量交叉偶联以良好的收率进行，但到目前为止，催化转换尚未被证实。

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