Free Radical Alkylation Of Heteroarenes And Quinones With Alcohols And Olefins

Phenanthridines and quinones exist widely in nature,which are the core framework of many drug molecules and have wide application value and potential in the medical field.Although great breakthroughs have been made in synthetic methodologies in recent decades,greener and more efficient methods are still desired.In this paper,A wide range of alkylated phenanthridines and quinones can be rapidly synthesized by using readily available and inexpensive alcohols and olefins as alkyl radical precursors.This paper mainly discusses from the following three aspects:1.Several major transformation pathways of alcoholsA free radical promoted four kinds of transformation pathways of alcohols were introduced.And these transformation mechanisms are analyzed and demonstrated in detail.The experimental and computed results could explain when and why one pathway occurs well.Hence it might be instructive and valuable for field of radical C-C bond formation with alcohol.2.Four pathways in radical alkylation of isocyanide with alcoholCopper catalyzed four pathways in radical alkylation of isocyanide with simple alcohol in the presence of dicumyl peroxide by using alcohols as alkyl radical precursors were described.Through the regulation of temperature,the reaction pathway can be controlled so as to control the reaction products.Furthermore,a reliable reaction mechanism was proposed by capturing free radical intermediates in the reaction process by electron paramagnetic resonance?EPR?.3.Free radical alkylation of quinones and olefinsWe demonstrated herein an Fe?III?-mediated radical alkylation of quinones.A wide range of bioactive molecules with quinone motifs can be rapidly synthesized by using readily available and inexpensive NaBH₄/NaBD₄ with alkenes at room temperature under open flask conditions.And the reaction can be scaled up to the gram scale without affecting its efficiency,so the scalability is very well.In this paper,detailed condition optimization,extensive substrate expansion,practical synthesis application and detailed mechanism verification are carried out.Figure[43]table[10]reference[118]...