Regio- and Diastereoselective Highly Strained Alkylidenecyclobutane Isomerization/Hydroacylation: Synthesis of Multisubstituted Cyclobutanes with Consecutive Stereocenters

作者：Tian, Kai-Qiang; Zhang, Shi-Jiao; Zhao, Jun; Duan, Gui-Yun; Wang, Qiao-Ling; Cui, Guo-Hao; Guo, Rui^*; Li, Hong-Shuang^*

来源：ACS Catalysis, 2024, 14(3): 1505-1513.

DOI：10.1021/acscatal.3c05616

• alkylidenecyclobutane
• alkeneisomerization
• hydroacylation
• selectivity
• rhodium catalysis

The regio- and diastereoselective alkene isomerization and hydrofunctionalization sequence enabled by transition-metal complexes allows rapid activation and assembly of the C-(sp(3))-H bond that is either adjacent or distal to the initial double bond, which has been a longstanding challenge in this field. Herein, we develop unusual rhodium-catalyzed isomerization of alkylidenecyclobutanes with subsequent hydroacylation reaction to provide multisubstituted cyclobutanes with continuous stereocenters. Note that this tandem process features a good regio- and diastereoselectivity profile. Isotopic labeling experiments support the "exo to endo" migration of the double bond to a coordinated cyclobutene that is responsible for the deuterium incorporation observed in the cyclobutane product.

• 单位
  山东省医学科学院; 青岛大学