School of Chemistry & Materials Science, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials , Jiangsu Normal University , Xuzhou , 221116 , P. R. China.
Org Lett. 2018 Jun 15;20(12):3596-3600. doi: 10.1021/acs.orglett.8b01382. Epub 2018 Jun 1.
A new combination of " anti-Baldwin" 3- exo-dig cyclization with 1,2-alkynyl migration of 1,4-enynes with simple cycloalkanes was established, enabling C-C breaking and reconstruction to access a wide range of α-alkynyl ketones with generally good yields by FeCl/di- tert-butyl peroxide (DTBP) as a catalytic oxidation system. Radical-induced C(sp)-H functionalization of cycloalkanes was realized, leading to the direct formation of C(sp)-C(sp) and C(sp)-C(sp) bonds. The mechanism for forming α-alkynyl ketones was proposed.
建立了一种新的“反鲍德温”3-endo-二氢环化与 1,4-烯炔的 1,2-炔基迁移的组合，该组合使用简单的环烷烃，通过 FeCl/二-叔丁基过氧化物 (DTBP) 作为催化氧化体系，实现了 C-C 的断裂和重建，从而以通常良好的收率获得了广泛的α-炔基酮。还实现了环烷烃的自由基诱导 C(sp)-H 官能化，从而直接形成 C(sp)-C(sp)和 C(sp)-C(sp)键。提出了形成α-炔基酮的反应机理。
