Divergent Synthesis of β-Fluoroamides via Silver-Catalyzed Oxidative Deconstruction of Cyclopropanone Hemiaminals.
Divergent Synthesis of β-Fluoroamides via Silver-Catalyzed Oxidative Deconstruction of Cyclopropanone Hemiaminals.
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通过环丙酮半缩醛的银催化氧化解构β-氟酰胺的发散合成。
DOI：
10.1021/acs.orglett.3c01992
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发表时间：
2023
期刊：
影响因子：
5.2
通讯作者：
Lindsay,VincentNG
中科院分区：
文献类型：
--
作者：
Jang,Yujin;Deng,Weixia;Sprague,IvanS;Lindsay,VincentNG
报道了一种从容易获得的环丙酮等价物合成具有挑战性的β-氟酰胺的简便方法。在添加此处用作瞬时离去基团的吡唑之后，所得半缩醛胺的银催化的区域特异性开环缩合产生对胺取代反应的β-氟化N-酰基吡唑中间体，最终得到β-氟酰胺。该方法还可以扩展到通过分别添加醇或β-氟代醇作为末端亲核试剂来合成β-氟代酯和γ-氟代醇。
An expedient approach for the synthesis of challenging β-fluoroamides from readily accessible cyclopropanone equivalents is reported. Following the addition of pyrazole used here as a transient leaving group, silver-catalyzed regiospecific ring-opening fluorination of the resulting hemiaminal leads to a β-fluorinatedN-acylpyrazole intermediate reactive to substitution with amines, ultimately affording β-fluoroamides. The process could also be extended to the synthesis of β-fluoroesters and γ-fluoroalcohols via the addition of alcohols or hydrides as terminal nucleophiles, respectively.