The Development Of Novel Methods To Construct C(sp~2)-P Bonds

Aromatic organophosphorus compounds have attracted considerableinterest due to their wide applications in various fields. Thereforecontinuing efforts have been made to construct C(sp2)–P bonds. Althoughvarious pathways to prepare arylphosphine and their derivatives have beenreported, it is still worth to explore more efficient methods. My thesis isfocused on developing novel methods to construct C(sp2)-P bondsincluding transition metal-catalyzed cross-coupling and transitionmetal-free synthesis of arylphosphorus compounds. The research work isdivided into three parts.The first part is about nickel-catalyzed C–P coupling of arylmesylates and tosylates with H(O)PR1R2. Utilizing stable and readilyavailable aryl mesylates and tosylates as substrates, we have developed amethod for C(sp2)–P coupling via nickel-catalyzed cross-coupling withH(O)PR1R2to prepare arylphosphonates, diarylphosphinates, andarylphosphine oxides. To the best of our knowledge, this is the firstexample of nickel-catalyzed C–P coupling of aryl mesylates and tosylates.The second part is about developing an efficient and practicalpathway to obtain various arylphosphorus compounds by taking advantageof nucleophilic addition of nucleophilic phosphorus reagents to in-situgenerated aryne intermediates.The third part is about inserting arynes into arylphosphoryl amide bonds to simultaneously construct C-N and C-P bonds in one step. Theprocess provides a simple way to produce o-amine-substitutedarylphosphine oxides which are some precursors for a number of bidentateaminophosphine ligands...