Radical Transformations Of Katritzky Salts And Cycloketone Oxime Esters

Primary amines are not only ubiquitous in organic molecules and natural products but also widely present as structural motifs in bioactive agents.Notably,they frequently serve as building blocks in organic synthesis.Bench-stable and easily handled Katritzky salts can be prepared from a-Amino acids and their derivatives but also can be prepared from primary amines in one step.Katritzky salts provide a new method for the generation of alkyl radicals via C(sp3)-N bond activation.Cyclobutanones and their derivatives are very useful synthons that are widely used in total synthesis of nature products,which could be formed under very mild conditions.In this thesis,I focus on radical allylation with Katritzky salts as radical precursors.Moreover,a C-C bond cleavage and free radical cascade addition with cycloketone oxime esters was studied and a high-efficiency for the synthesis of useful alkyl nitriles was developed.I focus on radical allylation with Katritzky salts as radical precursors.(1)Katritzky salts as radical precursorsIn this section,we describe a visible-light-mediated allylation reaction of Katritzky salts with allyl sulfones via a deaminative strategy.With Ir[(ppy)2(dtbbpy)]PF6 as the photocatalyst and i-Pr2NEt as the reductant,this mild approach provides ready access to site-specific C(sp3)-C(sp3)bond formation using abundant feedstock primary amines,particularly a-amino acids as alkyl radical precursors.(2)Cycloketone oxime esters as radical precursorsIn this part,we developed a radical addition of cycloketone oxime esters onto vinyl pyridine compound with 22 W blue light as the light source and HE as an electron and hydrogen donor.A variety of alkyl nitriles were synthesized.In addition,we also synthesized linear alkenyl nitriles with cycloketone oxime ester as radical sources.