Parameterization of Arynophiles: Experimental Investigations towards a Quantitative Understanding of Aryne Trapping Reactions
Parameterization of Arynophiles: Experimental Investigations towards a Quantitative Understanding of Aryne Trapping Reactions
复制标题
亲芳基的参数化：定量理解芳炔捕获反应的实验研究
DOI：
10.1055/a-1845-3066
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Stuart, David R.
中科院分区：
文献类型：
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作者：
Metze, Bryan E.;Bhattacharjee, Avik;McCormick, Theresa M.;Stuart, David R.
芳炔是高度反应性的中间体，其可通过用亲芳试剂捕获而策略性地用于合成。然而，这种试剂的“亲芳性”几乎完全是轶事，预测哪种试剂将是有效的陷阱往往是具有挑战性的。在这里，我们描述了一个系统的研究parameterized arynophilicity的广泛的试剂已知的陷阱arynes。以呋喃为参比亲芳体，3-氯苄基为芳炔，基于一锅竞争实验，提出了一个相对反应性标度。在周环反应、亲核加成和σ-键插入反应中反应的超过15种亲芳体用亲芳性（A）值参数化，并且多种芳炔前体是适用的。
Arynes are highly reactive intermediates that may be used strategically in synthesis by trapping with arynophilic reagents. However, ‘arynophilicity’ of such reagents is almost completely anecdotal and predicting which ones will be efficient traps is often challenging. Here, we describe a systematic study to parameterize the arynophilicity of a wide range of reagents known to trap arynes. A relative reactivity scale, based on one-pot competition experiments, is presented by using furan as a reference arynophile and 3-chlorobenzyne as a the aryne. More than 15 arynophiles that react in pericyclic reactions, nucleophilic addition, andσ-bond insertion reactions are parameterized with arynophilicity (A) values, and multiple aryne precursors are applicable.