Eberhart Andrew J, Shrives Harry J, Álvarez Estela, Carrër Amandine, Zhang Yuntong, Procter David J
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (UK), Fax: (+44) 161-275-4939 http://people.man.ac.uk/∼mbdssdp2/
Chemistry. 2015 May 11;21(20):7428-34. doi: 10.1002/chem.201406424. Epub 2015 Mar 6.
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.
一种由亚砜导向的芳烃和杂芳烃无金属邻位炔丙基化反应，利用分子间将炔丙基亲核试剂传递至硫原子，随后进行分子内传递至碳原子的过程。该操作简单的交叉偶联程序具有通用性，对炔丙基亲核试剂具有区域选择性，并且对邻位炔丙基化产物相对于联烯基化产物表现出完全的选择性。使用仲炔丙基硅烷可实现无金属邻位偶联，从而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“安全扣”性质在选择性、迭代双交叉偶联过程中得到了体现。炔丙基化产物是多功能中间体，并且它们已很容易地转化为取代苯并噻吩。
