Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has becom...Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has become important in the field of organic synthesis.Herein we report a general and modular method for the construction of P-stereogenic centers via palladium/chiral norbornene cooperative catalysis-enabled desymmetrization/kinetic resolution process.It is a two-component annulation reaction that involves widely available aryl iodides and prochiral or racemic phosphinamides as the reactants.A wide variety of substrates bearing an assortment of functional groups(50 examples)are compatible with this method.Other features include a distinct enantiodiscrimination mechanism,excellent stereoselectivities,and scalability.The obtained chiral P-stereogenic products bear a common C–Br bond,which can be elaborated for the synthesis of new P-stereogenic compounds with diverse structural features.In addition,preliminary studies uncover the promising chiroptical properties of these P-stereogenic cyclic phosphinamides.Density functional theory calculations are performed to reveal that the noncovalent hydrogen bonding interaction is the origin of enantiodiscrimination during the desymmetrization process.展开更多
基金the National Key Research and Development Program of China(grant no.2022YFA1503703)the National Natural Science Foundation of China(grant no.22325106)the Fundamental Research Funds for the Central Universities(grant no.2042024kf1014),and Wuhan University for financial support.
文摘Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has become important in the field of organic synthesis.Herein we report a general and modular method for the construction of P-stereogenic centers via palladium/chiral norbornene cooperative catalysis-enabled desymmetrization/kinetic resolution process.It is a two-component annulation reaction that involves widely available aryl iodides and prochiral or racemic phosphinamides as the reactants.A wide variety of substrates bearing an assortment of functional groups(50 examples)are compatible with this method.Other features include a distinct enantiodiscrimination mechanism,excellent stereoselectivities,and scalability.The obtained chiral P-stereogenic products bear a common C–Br bond,which can be elaborated for the synthesis of new P-stereogenic compounds with diverse structural features.In addition,preliminary studies uncover the promising chiroptical properties of these P-stereogenic cyclic phosphinamides.Density functional theory calculations are performed to reveal that the noncovalent hydrogen bonding interaction is the origin of enantiodiscrimination during the desymmetrization process.
