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Coordinating activation strategy for C(sp(3))-H/C(sp(3))-H cross-coupling to access β-aromatic α-amino acids.
Nature Communications ( IF 14.7 ) Pub Date : 2015-Sep-29 , DOI: 10.1038/ncomms9404
Kaizhi Li , Qian Wu , Jingbo Lan , Jingsong You
Nature Communications ( IF 14.7 ) Pub Date : 2015-Sep-29 , DOI: 10.1038/ncomms9404
Kaizhi Li , Qian Wu , Jingbo Lan , Jingsong You
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The past decade has witnessed significant advances in C-H bond functionalizations with the discovery of new mechanisms. Non-precious transition-metal-catalysed radical oxidative coupling for C(sp(3))-H bond transformations is an appealing strategy for C-C bond formations. The radical oxidative C(sp(3))-H/C(sp(3))-H cross-coupling reactions of α-C(sp(3))-H bonds of amines with free radicals represent a conceptual and practical challenge. We herein develop the coordinating activation strategy to illustrate the nickel-catalysed radical oxidative cross-coupling between C(sp(3))-H bonds and (hetero)arylmethyl free radicals. The protocol can tolerate a rich variety of α-amino acids and (hetero)arylmethanes as well as arylmethylenes and arylmethines, affording a large library of α-tertiary and α-quaternary β-aromatic α-amino acids. This process also features low-cost metal catalyst, readily handled and easily removable coordinating group, synthetic simplicity and gram-scale production, which would enable the potential for economical production at commercial scale in the future.
中文翻译:
C(sp(3))-H / C(sp(3))-H交叉偶联以访问β-芳族α-氨基酸的协调活化策略。
在过去的十年中,随着新机制的发现,CH键功能化取得了重大进展。C(sp(3))-H键转换的非贵重过渡金属催化的自由基氧化偶联是CC键形成的一种有吸引力的策略。胺的α-C(sp(3))-H键与自由基的自由基氧化C(sp(3))-H / C(sp(3))-H交叉偶联反应代表了概念上和实际上的挑战。我们在本文中开发了配位活化策略,以说明C(sp(3))-H键和(杂)芳基甲基自由基之间的镍催化的自由基氧化交叉偶联。该方案可以耐受多种α-氨基酸和(杂)芳基甲烷以及芳基亚甲基和芳基次甲基,从而提供了一个庞大的α-叔和α-季铵基β-芳族α-氨基酸文库。
更新日期:2015-10-02
中文翻译:

C(sp(3))-H / C(sp(3))-H交叉偶联以访问β-芳族α-氨基酸的协调活化策略。
在过去的十年中,随着新机制的发现,CH键功能化取得了重大进展。C(sp(3))-H键转换的非贵重过渡金属催化的自由基氧化偶联是CC键形成的一种有吸引力的策略。胺的α-C(sp(3))-H键与自由基的自由基氧化C(sp(3))-H / C(sp(3))-H交叉偶联反应代表了概念上和实际上的挑战。我们在本文中开发了配位活化策略,以说明C(sp(3))-H键和(杂)芳基甲基自由基之间的镍催化的自由基氧化交叉偶联。该方案可以耐受多种α-氨基酸和(杂)芳基甲烷以及芳基亚甲基和芳基次甲基,从而提供了一个庞大的α-叔和α-季铵基β-芳族α-氨基酸文库。
