4-氨基苯并三氮唑（ABTA）作为钯催化有氧氧化 C-H 烯烃化反应的可去除导向基团。
4-Aminobenzotriazole (ABTA) as a Removable Directing Group for Palladium-Catalyzed Aerobic Oxidative C-H Olefination.
机构信息
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Jilin, Changchun 130012, P. R. hina.
Department of Chemistry, University of South Florida, Tampa, Florida 33620, United States.
出版信息
Org Lett. 2022 May 6;24(17):3107-3112. doi: 10.1021/acs.orglett.2c00285. Epub 2022 Mar 24.
Abstract
4-Aminobenzotriazole (ABTA) was applied as an effective removable directing group (DG) in Pd-catalyzed C-H activation for the first time. Compared with the widely applied pyridine and quinoline analogs, ABTA showed significantly improved reactivity, achieving aerobic oxidative C-H olefination in excellent yields (up to 95% vs <50% with other reported DGs under identical conditions). Using this new strategy, macrocyclization was achieved to give cyclic peptides in good yields with easy ABTA removal under mild conditions, highlighting the promising potential of this new DG.
摘要
4-氨基苯并三氮唑（ABTA）首次被应用于钯催化的 C-H 活化中作为一种有效的可去除导向基团（DG）。与广泛应用的吡啶和喹啉类似物相比，ABTA 表现出显著提高的反应活性，在有氧氧化 C-H 烯烃化反应中可获得优异的产率（高达 95%，而在相同条件下使用其他报道的 DG 仅获得<50%的产率）。利用这种新策略，在温和条件下通过简单地去除 ABTA 可以实现大环化反应，得到环状肽，产率良好，这突出了这种新 DG 的有前景的潜力。
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2
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3
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Acc Chem Res. 2021 Jun 15;54(12):2750-2763. doi: 10.1021/acs.accounts.1c00168. Epub 2021 May 21.
5
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