Rh(iii)-catalyzed tandem annulative redox-neutral arylation/amidation of aromatic tethered alkenes.
Rh(iii)-catalyzed tandem annulative redox-neutral arylation/amidation of aromatic tethered alkenes.
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Rh(iii)-催化芳香族系链烯烃的串联环氧化还原中性芳基化/酰胺化
DOI：
10.1039/d0sc04007j
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发表时间：
2020-10-16
期刊：
影响因子：
8.4
通讯作者：
Zhou B
中科院分区：
文献类型：
--
作者：
Chen C;Shi C;Yang Y;Zhou B
过渡金属催化的定向 C-H 官能化已成为构建 C-C 键和 C-N 键的强大而直接的工具。在这些过程中，分子内环化烯烃加氢芳基化反应备受关注，因为这种分子内环化可以产生在众多天然产物和生物活性分子中发现的更复杂和高附加值的结构基序。尽管取得了显着的进展，但迄今为止开发的这些环形方案仍然仅限于烯烃一侧的加氢芳基化和官能化，从而在很大程度上限制了结构的多样性和复杂性。在此，我们开发了一种铑(iii)催化的芳香族系链烯烃的串联环化芳基化/酰胺化反应，通过使用3-取代的1,4,2-二恶唑-5-酮作为酰胺化试剂来捕获瞬态C(sp3)-Rh中间体，从而产生各种带有全碳季立体中心的2,3-二氢-3-苯并呋喃甲胺衍生物。值得注意的是，通过简单地改变导向基团，可以实现第二次不对称邻位C-H酰胺化/环化，从而以良好的产率提供三环二氢呋喃并[3,2-f]喹唑啉酮。开发了铑(iii)催化的芳香族系链烯烃的串联环芳基化/酰胺化反应，以产生多种2,3-二氢-3-苯并呋喃甲胺衍生物。
Transition-metal-catalyzed directed C–H functionalization has emerged as a powerful and straightforward tool to construct C–C bonds and C–N bonds. Among these processes, the intramolecular annulative alkene hydroarylation reaction has received much attention because this intramolecular annulation can produce more complex and high value-added structural motifs found in numerous natural products and bioactive molecules. Despite remarkable progress, these annulative protocols developed to date remain limited to hydroarylation and functionalization of one side of alkenes, thus largely limiting the structural diversity and complexity. Herein, we developed a rhodium(iii)-catalyzed tandem annulative arylation/amidation reaction of aromatic tethered alkenes to deliver a variety of 2,3-dihydro-3-benzofuranmethanamine derivatives bearing an all-carbon quaternary stereo center by employing 3-substituted 1,4,2-dioxazol-5-ones as an amidating reagent to capture the transient C(sp3)–Rh intermediate. Notably, by simply changing the directing group, a second, unsymmetrical ortho C–H amidation/annulation can be achieved to provide tricyclic dihydrofuro[3,2-f]quinazolinones in good yields. A rhodium(iii)-catalyzed tandem annulative arylation/amidation reaction of aromatic tethered alkenes was developed to deliver a variety of 2,3-dihydro-3-benzofuranmethanamine derivatives.
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影响因子：
5.2
作者：
Grohmann, Christoph;Wang, Honggen;Glorius, Frank
通讯作者：
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62.1
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作者：
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通讯作者：
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