Shukla Rahul K, Chaturvedi Atul K, Pal Subir, Volla Chandra M R
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Org Lett. 2021 Feb 19;23(4):1440-1444. doi: 10.1021/acs.orglett.1c00118. Epub 2021 Feb 2.
Herein we demonstrate a Pd(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes. The σ-vinyl-palladium(II) intermediate generated by the -acetoxypalladation of alkynes was added across carbon-carbon double bond to realize an efficient hydroalkenylation protocol. Bidentate auxiliary 8-aminoquinoline controls the regioselectivity of the carbopalladation step and thereby controls the regioselectivity of the hydroalkenylation. Additionally, when alkynes containing a hydroxy group at the three- or four-position were employed, the cascade sequence led to 1,6-dicarbonyl compounds via hydroalkenylation followed by intramolecular acyl migration.
在此，我们展示了一种钯（II）催化的未活化烯烃的区域选择性碳氢官能化反应。通过炔烃的乙酰氧基钯化反应生成的σ-乙烯基钯（II）中间体与碳-碳双键加成，实现了一种高效的氢烯基化反应方案。双齿助剂8-氨基喹啉控制碳钯化步骤的区域选择性，从而控制氢烯基化反应的区域选择性。此外，当使用在3-或4-位含有羟基的炔烃时，级联反应序列通过氢烯基化反应，随后进行分子内酰基迁移，生成1,6-二羰基化合物。
