The transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines: access to (Z)-3-(silylmethylene)indolin-2-ones

作者：Han, Ya-Fei; Lv, Gui-Fen; Li, Yang^*; Wu, Li-Jun^*; Ouyang, Xuan-Hui; Li, Jin-Heng^*

来源：Chemical Science, 2022, 13(32): 9425-9431.

DOI：10.1039/d2sc03009h

• CATALYZED CYCLIZATION REACTION
• C-H FUNCTIONALIZATION
• 2-(ALKYNYL)ARYL ISOCYANATES
• SELECTIVE SYNTHESIS
• OXINDOLE SYNTHESIS
• NATURAL-PRODUCTS
• BOND ACTIVATION
• 3-ALKYLIDENEOXINDOLES
• DERIVATIVES
• CLEAVAGE

A new method involving mild acryl transient-chelating-group-controlled stereoselective Rh(i)-catalyzed silylative aminocarbonylation of 2-alkynylanilines with CO and silanes is presented for producing (Z)-3-(silylmethylene)indolin-2-ones. Upon using an acryl transient chelating group, 2-alkynylanilines undergo an unprecedented alkyne cis-silylrhodation followed by aminocarbonylation to assemble (Z)-3-(silylmethylene)indolin-2-ones. Mechanistic studies show that acryl transient chelating effects result in the key alkyne cis-silylrhodation process.

• 单位
  兰州大学; y; 云南大学; 南昌航空大学