Achieving Site Selectivity in Metal-Catalyzed Electron-Rich Carbene Transfer Reactions from N-Tosylhydrazones

作者：Su, Naijing; Deng, Tianning; Wink, Donald J.; Driver, Tom G.^*

来源：Organic Letters, 2017, 19(15): 3990-3993.

DOI：10.1021/acs.orglett.7b01694

• C-H INSERTION
• ALPHA-DIAZOCARBONYL COMPOUNDS
• BOND-DISSOCIATION ENERGIES
• INTERMOLECULAR REACTIONS
• EQUILIBRIUM ACIDITIES
• DIMETHYL-SULFOXIDE
• FUNCTIONALIZATION
• HETEROCYCLES
• MIGRATION
• AMINATION

Catalyst control of the site-selectivity of electron-rich alkyl, aryl disubstituted carbenes generated in situ from o-alkenyl-substituted N-tosylhydrazones was achieved in this study. Exposure of these substrates to copper iodide triggered the formation of alpha-alkoxy 2H-naphthalenones. This investigation established that changing the catalyst to a rhodium(II) carboxylate turned off cyclization and migration of the electron-rich metal carbene with the beta-carboxylate and turned on allylic C-H bond functionalization to diastereoselectively afford 1H-indenes. Examination of the scope of this reaction revealed that ethereal, aminomethylene, and unactivated 2 degrees C-H bonds could be functionalized.

• 出版日期2017-8-4
• 单位华侨大学