Visible-light Photocatalyzed Intermolecular Oxyamination Of Alkenes And TEMPO-Promoted Radical Ring-Opening Of Cyclopropanols

Carbon-heteroatom bonds(such as C-N,C-O,C-Si,C-P,etc.)are the most common chemical bonds in organic molecules.Their construction is an important step in the synthesis of drug molecules,natural products,functional materials,etc.,and also the key to further functional group transformation.For a long time,chemists are highly focused on the construction of carbon-heteroatom bonds,which leads to the emergence of many methods for the construction of carbon-heteroatom bonds.These methods mainly focus on the cross-coupling reactions catalyzed by transition metals with aryl or alkyl halides and heteroatom nucleophiles as substrates.At the same time,these methods have been applied to the synthesis of many bulk chemicals,such as amines,esters,aldehydes,ketones,phosphates and heterocyclic compounds.However,these methods still have many problems,such as harsh reaction conditions,limited substrate sources,and transition metal residues,and their applications in many fields such as the pharmaceutical industry have certain limitations.Therefore,the exploration of more green and efficient methods for the construction of carbon-heteroatom bonds under mild conditions to realize the facile synthesis of functional compounds containing heteroatom is still needed.In this thesis,the efficient constructions of C-N/C-O bonds and C-P bonds have been achieved successfully by using visible light-promoted vicinal oxyamination of alkenes and radical-mediated cyclopropanol ring-opening phosphating,respectively.The contents include the following parts:In the literature review part,it briefly introduces the importance of ?-amino alcohol compounds and their applications in medicine and organic synthesis.Then the synthesis of ?-amino alcohol compounds via the aminoxygenation and oxyamination of alkenes are briefly summarized.In the second part,a mild and simple method for the synthesis of ?-amino alcohol derivatives by intermolecular oxyamination of alkenes has been developed by using ketoxime carbonates as the bifunctional reagents under visible-light promoted photocatalytic energy transfer conditions.In the third part,a simple protocol for the synthesis of a series of ?-carbonyl phosphine compounds has been developed by using cyclopropanol and trialkyl phosphite as the substrates and TEMPO(2,2,6,6-Tetramethylpiperidine 1-oxyl)as the oxidant.In this process,?,?-unsaturated ketones as the key intermediates are produced by the ring-opening of the in-situ formed cyclopropanol radical via the oxidation of cyclopropanols by TEMPO.Finally,the addition of triethyl phosphite onto ?,?-unsaturated ketone realizes the C-P bond construction.