Merging “<i>Anti</i>-Baldwin” 3-<i>Exo-Dig</i> Cyclization with 1,2-Alkynyl Migration for Radical Alkylalkynylation of Unactivated Olefins
作者:Qi Zhao、Xiao-Shuang Ji、Yi-Yun Gao、Wen-Juan Hao、Ke-Ying Zhang、Shu-Jiang Tu、Bo Jiang
DOI:10.1021/acs.orglett.8b01382
日期:2018.6.15
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 FeCl2/di-tert-butyl peroxide (DTBP) as a catalytic oxidation system. Radical-induced C(sp3)–H functionalization of cycloalkanes was realized, leading to the direct formation of C(sp3)–C(sp3)
建立了“反鲍德温” 3-外切-环化与简单环烷烃与1,4-烯炔的1,2-炔基迁移的新组合,从而使C–C断裂和重建能够获得广泛的α-炔基FeCl 2 /二叔丁基过氧化物(DTBP)作为催化氧化系统,其酮的收率通常良好。自由基引起的环烷烃的C(sp 3)–H官能化得以实现,从而直接形成C(sp 3)–C(sp 3)和C(sp)–C(sp 3)键。提出了形成α-炔基酮的机理。