Overturning established chemoselectivities: selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors.
Overturning established chemoselectivities: selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors.
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DOI：
10.1021/ja4050168
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发表时间：
2013-07-31
影响因子：
15
通讯作者：
Murphy, John A.
中科院分区：
文献类型：
--
作者：
Doni, Eswararao;Mondal, Bhaskar;O'Sullivan, Steven;Tuttle, Tell;Murphy, John A.
基于金属的还原剂，包括金属、金属络合物和金属盐的流行，产生了支配我们的化学合成方法的反应性的经验顺序。然而，这种反应性可能会受到稳定的过渡态，中间体，和产品通过基板金属键合。本文报道，在没有这种稳定的相互作用，建立化学选择性可以被推翻。因此，最近开发的中性有机超电子供体5的光活化在活化的酯和腈的存在下选择性地还原烷基取代的苯环，与基于金属的还原形成直接对比，打开了关于反应性的新视角。有机给电子体引起的改变的结果归因于中性有机给电子体和底物的芳烃环之间的选择性相互作用。
The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate–metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.
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影响因子：
3
作者：
Grimme, Stefan
通讯作者：
Grimme, Stefan
影响因子：
3.6
作者：
BENKESER, RA;BELMONTE, FG;KANG, J
通讯作者：
KANG, J
影响因子：
2
作者：
Garnier, Jean;Murphy, John A.;Turner, Andrew T.
通讯作者：
Turner, Andrew T.
影响因子：
1.8
作者：
KANG, HY;HONG, WS;KOH, HY
通讯作者：
KOH, HY
影响因子：
2.7
作者：
Garnier J;Thomson DW;Zhou S;Jolly PI;Berlouis LE;Murphy JA
通讯作者：
Murphy JA