Department of Chemistry , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.
J Am Chem Soc. 2019 Sep 4;141(35):13788-13794. doi: 10.1021/jacs.9b07582. Epub 2019 Aug 21.
The general enantioselective synthesis of axially chiral disubstituted allenes from prochiral starting materials remains a long-standing challenge in organic synthesis. Here, we report an efficient enantio- and chemoselective copper hydride catalyzed semireduction of conjugated enynes to furnish 1,3-disubstituted allenes using water as the proton source. This protocol is sufficiently mild to accommodate an assortment of functional groups including keto, ester, amino, halo, and hydroxyl groups. Additionally, applications of this method for the selective synthesis of monodeuterated allenes and chiral 2,5-dihydropyrroles are described.
从手性起始原料出发，实现轴手性二取代丙二烯的通用对映选择性合成仍然是有机合成中的一个长期挑战。在此，我们报告了一种高效的对映选择性和化学选择性铜氢化物催化的共轭烯炔的半还原反应，该反应以水为质子源，生成 1,3-二取代丙二烯。该方法条件温和，能够兼容各种官能团，包括酮、酯、氨基、卤基和羟基。此外，还描述了该方法在单氘代丙二烯和手性 2,5-二氢吡咯选择性合成中的应用。
