Liu Lei, Lee Wes, Youshaw Cassandra R, Yuan Mingbin, Geherty Michael B, Zavalij Peter Y, Gutierrez Osvaldo
Department of Chemistry and Biochemistry, University of Maryland College Park Maryland 20742 USA
Chem Sci. 2020 Jul 24;11(31):8301-8305. doi: 10.1039/d0sc02127j.
A highly chemoselective iron-catalyzed three-component dicarbofunctionalization of unactivated olefins with alkyl halides (iodides and bromides) and sp-hybridized Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp-hybridized nucleophiles (electron-rich and electron-deficient (hetero)aryl and alkenyl Grignard reagents), alkyl halides (tertiary alkyl iodides/bromides and perfluorinated bromides), and unactivated olefins bearing diverse functional groups including tethered alkenes, ethers, protected alcohols, aldehydes, and amines to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines a three-component radical cascade cyclization/arylation that forges three new C-C bonds.
报道了一种高度化学选择性的铁催化未活化烯烃与卤代烃（碘化物和溴化物）以及sp杂化格氏试剂的三组分双碳官能化反应。该反应在快速周转频率下进行，并且耐受多种sp杂化亲核试剂（富电子和缺电子的（杂）芳基和烯基格氏试剂）、卤代烃（叔烷基碘化物/溴化物和全氟溴化物）以及带有包括连接烯烃、醚、保护醇、醛和胺在内的多种官能团的未活化烯烃，以高区域选择性生成所需的1,2-烷基芳基化产物。此外，我们证明该方法适用于合成新的（杂）碳环，包括四氢呋喃和吡咯烷——一种形成三个新C-C键的三组分自由基级联环化/芳基化反应。
