Study Of Important Biochemical Reactions With Organic Phosphorus Compounds Participation:A Theoretical Study

Phosphorus is the essential element in entire living organisms on earth.Relevant research of phosphorus refer to many fields of science including chemistry and biology.Organic phosphorus compounds participate in many important biochemical reactions.There is vital biological sense to investigate relevant mechanisms of them.This assertion,based on theoretical study,tried to explain several biochemical reactions which organic phosphorus compounds participate in.High temperature and high pressure which is the feature of submarine hydrothermal solution system promote many biochemical reactions.Micromolecule became macromolecule,which was an important stage in the originating process of life,including the process of peptides formation.In the discussion of the influence of high temperature and pressure based on experiments,this assertion proposed a mechanism that amino acids became peptide and explained the necessity of high temperature and pressure.As for the supporting of bioinformatics,this assertion concluded that the P-N bond and the P-O bond all exist in the process of phosphoryl group transferring.Based on the precedent theoretical study of phosphorylation-amino acids,the author perfected a new mechanism that called 'volleyball mechanism',which has three basic states:P-N intermediate,P-O intermediate and the transferring of phosphoryl group,verified by DFT calculation.With the aid of density functional theory(DFT)calculations,we also explored the mechanisms based on two reactions involving ruthenium(?)-catalyzed phosphoryl-directed ortho-selective C-H bond activation.Two types products were synthesized depending on the nature of the phosphoryl groups,namely R2P(O)and RP(O)OH.For R2P(O),the overall catalytic cycle includes three basic steps:C-H bond activation,alkyne insertion and protonation.The oxidation state of Ru centers does not change during the catalytic process.However,in the case of RP(O)OH,the whole catalytic cycle involves four basic steps:CH bond activation,alkyne insertion,reductive elimination and recycling of catalyst.The hydroxy of RP(O)OH successfully triggers the Ru(?)/Ru(O catalytic cycle.In addition,we found that most of the steps featuring cationic intermediates and transition states,in line with the experimental results that additives AgSbF6 and KPF6 were required for improved yields.