Asymmetric Friedel Crafts Reaction Of Trifluoromethyl Ketones&Allylic And Propargylic Csp~3-H Oxidative Functionalization

Part I: A chrial phorsphoric acid-catalyzed asymmetric Friedel-Crafts alkylationof4,7-dihydroindoles and trifluoromethyl ketones has been developed. TheCF3-containing adducts are key intermediates in medicine and agrochemicals. A seriesof aromatization by-products were also isolated by us. In addition, theenantioenriched2-indolyl derivatives were produced by sequential oxidations.Part II: A direct approach to alkenyl aldehydes from simple alkenyl arenescatalyzed by iron salts via Csp3H functionalization has been developed. Varientsynthetic important alkenyl aldehydes have been produced in high yields. Themechanism studies indicate that the allylic Csp3H cleavage may be involved in therate determinating steps.Part III: A C O formation by oxidative dehydrogenative coupling betweenpropargylic azides and carboxylic acids has been disclosed. A cheap iron catalyst wasemployed to promote this mild coupling reaction, which gives interestingmulti-functionalized products. To demostrate the importance of our methodology insynthesis, many applications in building chemical and biological active compoundshave been successfully carried out. On the basis of the observation of controlledexperiments, the azido goup may play an important role in the propargylic Csp3Hactivation by the stabilization of carbocation intermediates.