Capaldo Luca, Ravelli Davide
Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
PhotoGreen Lab, Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy.
Org Lett. 2021 Mar 19;23(6):2243-2247. doi: 10.1021/acs.orglett.1c00381. Epub 2021 Mar 3.
A versatile approach for the alkynylation of a variety of aliphatic hydrogen donors, including alkanes, is reported. We used tetrabutylammonium decatungstate as photocatalyst to generate organoradicals from C-H/Si-H bonds via hydrogen atom transfer. The latter intermediates underwent SOMOphilic alkynylation by methanesulfonyl alkynes to afford internal alkynes upon loss of a sulfonyl radical. The effect of different radicofugal groups on the reaction outcome was evaluated and rationalized via a combined experimental and computational approach.
报道了一种用于多种脂肪族氢供体（包括烷烃）炔基化的通用方法。我们使用四丁基铵十钨酸盐作为光催化剂，通过氢原子转移从C-H/Si-H键生成有机自由基。后者的中间体通过甲磺酰基炔烃进行亲SOMO炔基化，在失去磺酰基自由基后得到内炔。通过实验和计算相结合的方法评估并合理化了不同离去基团对反应结果的影响。
