Metal-free Phosphorylation of C(sp~3)-H and S-H Bonds

Author:Wen Chun Xiao

Supervisor:zhang chen qian

Database:Doctor

Degree Year:2019

Download:15

Pages:263

Size:31930K

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Organophosphorus compounds are widely used in medicinal chemistry,pesticide chemistry,materials science,and as ligands,catalysts,etc.,while their traditional synthesis methods generally use phosphorus halogen reagents,nucleophilic substitution of organometallic reagents,but such reactions often face moisture-sensitive,requires pre-functionalization,harsh reaction conditions,and high toxicity limits.Based on the oxidative coupling of our group to construct the reaction of phosphorus-carbon,phosphorus-fluorine and phosphorus-oxygen bonds,the method of constructing phosphorus-carbon and phosphorus-heterobond for the development of simple,efficient and atomic economic strategies has been further explored.(1)We have developed a method for the synthesis of allylphosphonates use 1,3-diarylpropenes with P(O)H compounds by cross-dehydrogenation coupling at room temperature,a series of allylphosphonates were synthesized by this method.The substrates have a wide range of functional group tolerances and good yields.The corresponding conversion was achieved in scal-up reaction at a yield of 72%.The conversion strategy was convenient,efficient,and green.Finally,the possible reaction mechanism was proposed,it provides a theoretical basis and experimental basis for the green and efficient construction of C(sp3)-P bonds under mild conditions.(2)We have developed a method for the synthesis of cyclohepta-2,4,6-trien-l-ylphosphonates use cycloheptatriene with P(O)H compounds by cross-dehydrogenation coupling at room temperature,the substrates have a wide range of functional group tolerances and good yields,a series of cyclohepta-2,4,6-trien-l-ylphosphonates were synthesized by this method.The Michaelis-Arbuzov-type reaction of P(Ⅲ)compounds afford a facile access to dialkyl/diaryl tropylphosphonates.Based on the first part of the research,the possible reaction mechanism was proposed.We have developed a simple,efficient,green synthesis method for cycloheptatriene phosphorylation.(3)We have developed a method for the synthesis of phosphorothioates via halogen-and metal-free K2CO3-promoted aerobic oxidative cross-coupling of trialkyl phosphites,dimethyl phenylphosphonite or methyl diphenylphosphinite with thiophenols using air as the oxidant at room temperature,this transformation provides a straightforward route to the construction of phosphorus-sulfur bonds with wide functional group compatibility,which affords phosphorothioates in up to 94%yield.The corresponding conversion was achieved in scal-up reaction at a yield of 65%.Finally,the possible reaction mechanism was proposed.At the same time,we have developed a novel and efficient oxidation of thiophenols with TBHP/TBAI under mild conditions.This method provides a simple and practical protocol for the synthesis of tert-butyl arylsulfinates with good functional group compatibility.it provides an alternative path for the synthesis of tert-butyl arylsulfinates.