Visible Light-induced Sulfonylation Of Fluorinated Allenes

Allenes are a class of compounds containing 1,2-accumulative diene functional groups that are widely present in natural products.Control the reaction selectivity of allenes still becomes a challenging task by introducing of difluoromethylene phosphonate group into allenes which may change the electrons density of the accumulated diene.Sulfonyl groups are a special kind of functional groups that have been widely used in pesticides,materials and medicines.In recent years,visible light-induced reactions have attracted widespread attention among chemists due to their mild conditions and efficient conversion.The main purpose of this dissertation is to achieve visible light-induced sulfonylation of fluorine-containing allenes with high regio-and stereoselectivity by regulation of reaction conditions and substrates and to synthesize a series of novel multifunctional fluorine-containing phosphonates with potential bioactivities.The dissertation consists of following two parts:Part ?:Studies on the visible light-induced sulfonylation of ?,?-difluoromethylene-?-allenylphosphonates with sulfonyl chlorideUsing sulfonyl chloride as a sulfonyl radical source,the visible light-induced sulfonylation of ?,?-difluoromethylene-?-allenic phosphonates was studied.Through regulation of the different reaction conditions such as fac-Ir(ppy)3 or[Ir(ppy)2dtbbpy]PF6/NaHCO3,two kinds of structure novel multifunctional fluorine-containing phosphonates were prepared with high regio-and stereoselectivity.These reactions feature mild conditions,readily available sulfonylation reagents and broad substrate suitability.Part ?:Studies on the visible light-induced sulfonylation of ?,?-difluoromethylene-?-allenylphosphonates with sodium sulfinatesUsing sodium sulfinates as the source of sulfonyl radicals,the visible light-induced sulfonylation of ?,?-difluoromethylene-?-allenic phosphonates was investigated.A novel kind of multifunctional(E)-?-fluorovinylphosphonates was synthesized with high regio-and stereoselectivity via tandem sulfonylation-defluorination reaction under Ru(bpy)3Cl2·6H2O catalyst.This reaction features mild conditions,readily available sulfonylation reagents and broad substrate suitability.