Asymmetric intermolecular allylic C-H amination of alkenes with aliphatic amines
Asymmetric intermolecular allylic C-H amination of alkenes with aliphatic amines
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DOI：
10.1126/science.abq1274
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发表时间：
2022-12-16
期刊：
影响因子：
56.9
通讯作者：
Gevorgyan, Vladimir
中科院分区：
文献类型：
--
作者：
Cheung, Kelvin Pak Shing;Fang, Jian;Gevorgyan, Vladimir
脂肪族烯丙胺存在于多种复杂的生物相关分子中。烯烃的直接烯丙基 C-H 胺化是实现这些基序的最直接方法。然而，在这种转化中使用广泛使用的内烯烃与脂肪胺仍然是一个合成挑战。特别是，钯催化面临着双重挑战：Pd(II) 与内部烯烃的配位效率低下，但由于碱性脂肪胺对 Pd(II) 的配位过于紧密，因此抑制配位。我们报告了这些问题的通用解决方案。与经典的 Pd(II/0) 方案相比，所开发的方案通过蓝光诱导的 Pd(0/I/II) 歧管与温和的芳基溴氧化剂进行操作。这种开壳方法还能够实现对映和非对映选择性烯丙基 C-H 胺化。
Aliphatic allylic amines are found in a great variety of complex and biorelevant molecules. The direct allylic C-H amination of alkenes serves as the most straightforward method toward these motifs. However, use of widely available internal alkenes with aliphatic amines in this transformation remains a synthetic challenge. In particular, palladium catalysis faces the twin challenges of inefficient coordination of Pd(II) to internal alkenes but excessively tight and therefore inhibitory coordination of Pd(II) by basic aliphatic amines. We report a general solution to these problems. The developed protocol, in contrast to a classical Pd(II/0) scenario, operates through a blue light-induced Pd(0/I/II) manifold with mild aryl bromide oxidant. This open-shell approach also enables enantio-and diastereoselective allylic C-H amination.