Radical transfer hydroamination with aminated cyclohexadienes using polarity reversal catalysis:: Scope and limitations
Radical transfer hydroamination with aminated cyclohexadienes using polarity reversal catalysis:: Scope and limitations
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DOI：
10.1021/ja0692581
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发表时间：
2007-04-11
影响因子：
15
通讯作者：
Studer, Armido
中科院分区：
文献类型：
--
作者：
Guin, Joyram;Mueck-Lichtenfeld, Christian;Studer, Armido
本文报道了几种新的1-胺化-2，5-环己二烯的合成。这些试剂可用于未活化和富电子双键的自由基转移氢胺化。用硫醇作为极性反转催化剂，获得了良好的产率。自由基氢胺化以良好至优异的反马尔可夫尼科夫选择性发生。许多官能团如醇、甲硅烷基醚、膦酸酯、芳基溴、酰亚胺、酰胺以及酸性质子在反应条件下是容许的。DFT计算提供了甲硅烷基，烷基和胺基取代的环己二烯基自由基的芳构化，以产生相应的C-，Si-和N-为中心的自由基的见解。
The synthesis of various new 1-aminated-2,5-cyclohexadienes is described. These reagents can be used in radical transfer hydroaminations of unactivated and electron-rich double bonds. With thiols as polarity reversal catalysts good yields are obtained. The radical hydroamination occurs with good to excellent anti-Markovnikov selectivity. Many functional groups such as alcohols, silyl ethers, phosphonates, arylbromides, imides, amides, and also acidic protons are tolerated under the reaction conditions. DFT calculations provide insights into the aromatization of silyl, alkyl, and aminyl substituted cyclohexadienyl radicals to generate the corresponding C-, Si-, and N-centered radicals.