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Photoredox-Catalyzed Site-Selective α-C(sp3 )-H Alkylation of Primary Amine Derivatives.
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2019-02-15 , DOI: 10.1002/anie.201812227
Melissa A Ashley 1 , Chiaki Yamauchi 1 , John C K Chu 2 , Shinya Otsuka 1, 3 , Hideki Yorimitsu 3 , Tomislav Rovis 1, 2
Affiliation  

The synthetic utility of tertiary amines to oxidatively generate α‐amino radicals is well established, however, primary amines remain challenging because of competitive side reactions. This report describes the site‐selective α‐functionalization of primary amine derivatives through the generation of α‐amino radical intermediates. Employing visible‐light photoredox catalysis, primary sulfonamides are coupled with electron‐deficient alkenes to efficiently and mildly construct C−C bonds. Interestingly, a divergence between intermolecular hydrogen‐atom transfer (HAT) catalysis and intramolecular [1,5] HAT was observed through precise manipulation of the protecting group. This dichotomy was leveraged to achieve excellent α/δ site‐selectivity.

中文翻译:

光氧化还原催化的伯胺衍生物的位点选择性α-C(sp3)-H烷基化。

叔胺在氧化反应中产生α-氨基自由基的合成作用已得到很好的确立,但是由于竞争性副反应,伯胺仍然具有挑战性。本报告介绍了通过生成α-氨基自由基中间体对伯胺衍生物进行的位点选择性α-官能化。通过可见光光氧化还原催化,伯磺酰胺与缺电子的烯烃结合,可以有效,温和地构建C-C键。有趣的是,通过保护基团的精确操作,观察到分子间氢原子转移(HAT)催化与分子内[1,5] HAT之间的差异。利用这种二分法可实现出色的α/δ位点选择性。
更新日期:2019-02-15
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