Study On The New Methodology For The Formation Of P-C Bond Based On Difunctionalizations Of Alkyens And Chemical Model For The Origin Of The Genetic Code

Organic phosphorus-containing compounds are widely used in the fields of synthetic chemistry,ligand chemistry,life chemistry,materials chemistry and pharmaceutical chemistry.Therefore,the development of green and efficient methods to construct P-C bond is the long-awaited goal of scientists.With the development of modern organic chemistry,the transition-metal-catalyzed phosphorylation reaction and P-center radical reaction are regarded as the most efficient ways to construct organophosphine compounds using H-phosphite and secondary phosphine(P(O)H)as raw materials.It is noteworthy that through the radical-initiated phosphorus-related difunctionalization of unsaturated bond,the direct formation of a P-C bond and the introduction of other useful functional group in one step can be realized.In addition,phosphorus-containing heterocyclic compounds also be formed via a radical tandem cyclization strategy.Because alkynes are the most common raw materials used in academic research and industrial production,the first three parts of this paper focuse on the phosphinoyl-radical-initiated difunctionalization of alkynes.In the fourth part,we develop sulfonyl-radical-initiated sulfonylation/cyclization of alkynes.In the fifth part,we develop difluoroalkyl-radical-initiated phosphinodifluorcalkylation of alkynes.Since the origin of genetic code is a worldwide problem,the sixth part of the dissertation studies the chemical model of the origin of genetic code.The main contents of this thesis are as follows:1.We developed a new method for the synthesis of ?-Ketophosphonates and?-ketophosphine oxides.The synthesis of P-ketophosphonates has been achieved through silver-mediated direct oxyphosphorylation of terminal alkynes and H-phosphonates under aerobic conditions at room temperature.In the presence of CuSO4·5H2O and TBHP,the reaction of alkynyl acids with H-phosphine oxides could provide ?-ketophosphine oxides via phosphination/decarboxylation/oxidation.These two transformations allow the direct formation of a P-C bond and the construction of a keto group in one reaction under mild condition.2.We developed a new method for the synthesis of benzophosphole oxides.By using 2 mol%of CuSO4·5H20 as catalyst and 2.0 equive of TBHP as oxidant,alkynes could react with phenylphosphine oxides to generate benzophosphole oxides via radical oxidative phosphination-annulation.Most desired products could be obtained in good yields within 30 min.The method can be easily used in a large-scale preparation.3.We developed a new method for the synthesis of 3-phosphinoylquinolines.Only in the presence of TBHP without needing a metal,a base,and an additive,the reaction of N-propargylanilines with H-phosphine oxides could smoothly afford a series of substituted 3-phosphinoylquinolines via a phosphinoylation-cyclization-aromatization process.4.We developed a new method for the synthesis 2-sulfonated 9H-pyrrolo[1,2-a]indoles.By using sodium iodide as a catalyst and TBHP as an oxidant,N-propargyl-substituted indoles could react with sulfonyl hydrazides to synthesis of 2-sulfonated 9H-pyrrolo[1,2-a]indoles via a sulfonyl-radical-involved cascade cyclization-isomerization process.This green method can be easily used in a large-scale preparation and the C-S bond and the C-C bond could be formed in one pot.5.We developed a new method for the synthesis(E)-?,?-difluorovinylphosphine oxide derivatives.By using palladium(?)chloride as a catalyst and Xantphos as a ligand,the reaction of P(O)H compounds,alkynes,and ethyl difluoroiodoacetate proceeds with moderate to high yields.This reaction exhibited high stereoselectivities in favor of the E-isomers and allow the formation of C-P bond and C-CF2 bond in one step without external oxidant.6.We built up a simplified chemical model which only consists of phosphorous compounds,amino acids and nucleosides to study the origin of the genetic code.It was found that the yields of the "translation products",namely dipeptides,for each of the six amino acids(Phe,Trp,Tyr,His,Val and Leu)behaved differently with the presence of different nucleosides.The mechanism showed that the five-membered cyclic penta-coordiate nucleoside-phosphoric-amino acid anhydride(NPA)was the key intermediate.