Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202206692. doi: 10.1002/anie.202206692. Epub 2022 Jun 23.
The asymmetric hydroaminocarbonylation of olefins represents a straightforward approach for the synthesis of enantioenriched amides, but is hampered by the necessity to employ CO gas, often at elevated pressures. We herein describe, as an alternative, an enantioselective hydrocarbamoylation of alkenes leveraging dual copper hydride and palladium catalysis to enable the use of readily available carbamoyl chlorides as a practical carbamoylating reagent. The protocol is applicable to various types of olefins, including alkenyl arenes, terminal alkenes, and 1,1-disubstituted alkenes. Substrates containing a diverse range of functional groups as well as heterocyclic substructures undergo functionalization to provide α- and β-chiral amides in good yields and with excellent enantioselectivities.
烯烃的不对称氢氨基甲酰化反应是一种合成手性酰胺的直接方法，但需要使用 CO 气体，通常需要在高压下进行。在此，我们描述了一种替代方法，即利用双铜氢化物和钯催化的烯烃的对映选择性氢氨甲酰化反应，从而可以使用易得的氨基甲酰氯作为实用的氨基甲酰化试剂。该方案适用于各种类型的烯烃，包括烯基芳烃、末端烯烃和 1,1-二取代烯烃。含有各种官能团和杂环亚结构的底物进行官能化，以良好的收率和优异的对映选择性提供 α-和 β-手性酰胺。
