Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products.
Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products.
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DOI：
10.1002/anie.201308391
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发表时间：
2014-02-10
影响因子：
16.6
通讯作者：
Jamison, Timothy F.
中科院分区：
文献类型：
--
作者：
Tasker, Sarah Z.;Gutierrez, Alicia C.;Jamison, Timothy F.
在电子无偏烯烃的 Heck 反应中实现高选择性一直是一个长期的挑战。使用镍催化的阳离子 Heck 反应，我们能够对各种芳基亲电子试剂和脂肪族烯烃实现支化产物的优异选择性（在所有情况下≥19:1）。具有合适咬角和空间分布的双齿配体是获得高支化/线性选择性的关键，而合适的碱则抑制产物的烯烃异构化。虽然芳基三氟甲磺酸酯传统上用于进入阳离子 Heck 途径，但我们已经证明，通过使用三氟甲磺酸三乙基甲硅烷基酯 (TESOTf)，我们可以实现催化镍配合物的抗衡离子交换，从而可以使用更便宜且更稳定的芳基氯、甲磺酸酯、甲苯磺酸酯和氨基磺酸酯来以高选择性产生相同的支化产物。
Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, while the appropriate base suppressed alkene isomerization of the product. Though aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that by using triethylsilyl trifluoromethanesulfonate (TESOTf), we can effect a counterion exchange of the catalytic nickel complex such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity.
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