Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics.
Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics.
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DOI：
10.1002/chem.201406424
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发表时间：
2015-05-11
期刊：
影响因子：
--
通讯作者：
Procter DJ
中科院分区：
文献类型：
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作者：
Eberhart AJ;Shrives HJ;Álvarez E;Carrër A;Zhang Y;Procter DJ
芳族化合物和杂芳族化合物的亚砜导向的、无金属的邻位炔丙基化利用炔丙基亲核试剂到硫的分子间递送，随后是到碳的分子内中继。操作简单的交叉偶联程序是通用的，区域特异性的炔丙基亲核试剂，并显示出完整的选择性邻炔丙基化的丙二烯化的产品。仲炔丙基硅烷的使用允许无金属邻位偶联以在芳环和杂芳环与仲炔丙基中心之间形成碳-碳键。亚砜导向基团的“安全捕获”性质说明在一个选择性的，迭代的双交叉偶联过程。炔丙基化反应的产物是用途广泛的中间体，它们很容易转化为取代苯并噻吩。
A sulfoxide-directed, metal-free ortho-propargylation of aromatics and heteroaromatics exploits intermolecular delivery of a propargyl nucleophile to sulfur followed by an intramolecular relay to carbon. The operationally simple cross-coupling procedure is general, regiospecific with regard to the propargyl nucleophile, and shows complete selectivity for products of ortho-propargylation over allenylation. The use of secondary propargyl silanes allows metal-free ortho-coupling to form carbon–carbon bonds between aromatic and heteroaromatic rings and secondary propargylic centres. The ‘safety-catch’ nature of the sulfoxide directing group is illustrated in a selective, iterative double cross-coupling process. The products of propargylation are versatile intermediates and they have been readily converted into substituted benzothiophenes.