E-Olefins through intramolecular radical relocation
E-Olefins through intramolecular radical relocation
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DOI：
10.1126/science.aav1610
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发表时间：
2019-01-25
期刊：
影响因子：
56.9
通讯作者：
Schoenebeck, Franziska
中科院分区：
文献类型：
--
作者：
Kapat, Ajoy;Sperger, Theresa;Schoenebeck, Franziska
完全控制碳-碳双键迁移的选择性将使立体化学定义的烯烃成为制药、食品、香料、材料和石化领域的核心。过去60年研究的绝大多数双键迁移都是利用贵金属氢化物，这些氢化物通常与可逆平衡、氢混乱、不完全的E/Z立体选择和/或高成本有关。在这里，我们报告了一种完全不同的、基于激进的方法。我们展示了一种非贵重的，无还原剂的，原子经济的镍（Ni） 1 '催化分子内1,3-氢原子重新定位，在室温下3小时内生成e -烯烃。还演示了远距离安装e -烯烃。
Full control over the selectivity of carbon-carbon double-bond migrations would enable access to stereochemically defined olefins that are central to the pharmaceutical, food, fragrance, materials, and petrochemical arenas. The vast majority of double-bond migrations investigated over the past 60 years capitalize on precious-metal hydrides that are frequently associated with reversible equilibria, hydrogen scrambling, incomplete E/Z stereoselection, and/or high cost. Here, we report a fundamentally different, radical-based approach. We showcase a nonprecious, reductant-free, and atom-economical nickel (Ni)(l'-catalyzed intramolecular 1,3-hydrogen atom relocation to yield E-olefins within 3 hours at room temperature. Remote installations of E-olefins over extended distances are also demonstrated.