Radical 1,4-Aryl Migration Enabled Remote Cross-Electrophile Coupling of α-Amino-β-Bromo Acid Esters with Aryl Bromides,Angewandte Chemie International Edition

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Radical 1,4-Aryl Migration Enabled Remote Cross-Electrophile Coupling of α-Amino-β-Bromo Acid Esters with Aryl Bromides
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-07-21 , DOI: 10.1002/anie.202106273
Shi Tang ₁ , Zhen-Hua Xu ₁ , Ting Liu ₁ , Shuo-Wen Wang ₁ , Jian Yu ₁ , Jian Liu ₁ , Yu Hong ₁ , Shi-Lu Chen ₂ , Jin He ₁ , Jin-Heng Li _{3,

4}

Affiliation

We report an unprecedented, efficient nickel-catalysed radical relay for the remote cross-electrophile coupling of β-bromo-α-benzylamino acid esters with aryl bromides via 1,4-aryl migration/arylation cascades. β-Bromo-α-benzylamino acid esters are considered as unique molecular scaffolds allowing for aryl migration reactions, which are conceptually novel variants for the radical Truce–Smiles rearrangement. This reaction enables the formation of two new C(sp³)−C(sp²) bonds using a bench-stable Ni/bipyridine/Zn system featuring a broad substrate scope and excellent diastereoselectivity, which provides an effective platform for the remote aryl group migration and arylation of amino acid esters via redox-neutral C(sp³)−C(sp²) bond cleavage. Mechanistically, this cascade reaction is accomplished by combining two powerful catalytic cycles consisting of a cross-electrophile coupling and radical 1,4-aryl migration through the generation of C(sp³)-centred radical intermediates from the homolysis of C(sp³)−Br bonds and the switching of the transient alkyl radical into a robust α-aminoalkyl radical.

中文翻译：

自由基 1,4-芳基迁移使 α-氨基-β-溴酸酯与芳基溴的远程交叉电偶偶联成为可能

我们报告了一种前所未有的、高效的镍催化自由基中继，用于通过 1,4-芳基迁移/芳基化级联将 β-溴-α-苄基氨基酸酯与芳基溴进行远程交叉亲电偶联。β-溴-α-苄基氨基酸酯被认为是独特的分子支架，允许芳基迁移反应，这是自由基休战-微笑重排的概念新变体。该反应能够使用具有广泛底物范围和优异非对映选择性的长期稳定的 Ni/联吡啶/Zn 系统形成两个新的 C(sp ³ )-C(sp ² ) 键，为远程芳基提供了一个有效的平台氨基酸酯通过氧化还原中性 C(sp ³ )-C(sp ² ) 的迁移和芳基化) 键断裂。机械地，该级联反应由通过C（SP的产生相结合自由交亲电耦合和自由基1,4-芳迁移的两个强大的催化循环实现³）-centred从C的均裂自由基中间体（SP ³） -Br 键和瞬态烷基自由基转换为强大的 α-氨基烷基自由基。

更新日期：2021-09-14

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