Rhodium Or Ruthenium-Catalyzed C-7 Allylation Of Indoline Assisted By Directing Groups

The independent activation of C-H and C-C bonds is one of the two advanced synthetic strategies that organic chemists have mastered.Combining these two powerful strategies into a single tandem chemical process,provides new tool for overcoming synthetic challenges that could not be realized before,and develops more synthesis methods with step simplicity and atomic economy.Considering the application potential of simultaneous activation of C-H bond and C-C bond in organic synthesis,this paper mainly studied the preparation of C-7 indoline derivatives via sequential C-H and C-C bond activation using transition-metal rhodium or ruthenium catalyst.Specific research contents are as follows:1.Rhodium(?)-Catalyzed Direct C-7 allylation of Indolines via sequential C-H and C-C bond activation:An efficient,atom-economic method was developed for the preparation of C-7allylation of indoline derivatives with vinylcyclopropanes via sequential C-H and C-C bond activation using rhodium(?)catalyst.This reaction proceeds smoothly under mild conditions over a wide structural scope with excellent functional-group tolerance.This procedure allows for the efficient synthesis of 7-alkynyl-substituted indolines with pyrimidine as a directing group.2.Microwave-assisted Ru or Rh Catalyzed Direct C-7 allylation of Indolines via sequential C-H and C-C bond activation:An atom-economical C-7 allylation of indoline derivatives under microwave irradtion is described.In this transformation,using Ru or Rh catalyst with vinylcyclopropanes via sequential C-H and C-C bonds activation proceed at roomtemperature.Moreover,catalytic processes under solvent-free conditions greatly reduce the environmental impact and economic cost.The allylated indolines could be further improve the value-added via diversification.Therefore,microwave-promoted indole C7 allylation has high synthesis potential from both the perspective of sustainable development and environmental perspective.