For this work, we have selected two reactions for the formation of (2,2)-dichloro (ethyl) Arylphosphine and bis (2,2)-dichloro(ethyl)arylphosphine compounds by hydrophosphination. Global and local reactivity parameter...For this work, we have selected two reactions for the formation of (2,2)-dichloro (ethyl) Arylphosphine and bis (2,2)-dichloro(ethyl)arylphosphine compounds by hydrophosphination. Global and local reactivity parameters, thermodynamic parameters of reactions, Transition states, the Fukui function, the local softness, the local electrophility index, and nucleophility index, Natural population analyses (NPA) and Mulliken (MK) were calculated with DFT method at B3LYP/6-311+G(d, p) level. The analysis of potential energy surfaces and the nature of the reaction mechanism have been determined. The various results obtained revealed that the addition of Arylphosphine is regiospecific. The phenylphosphine is more stable than the thiophenylphosphine. The theoretical results are consistent with experience.展开更多
An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addit...An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addition under ultrasonic irradiation is described.This methodology provides a rapid and green approach for the construction of diarylmethyl phosphorus oxides bearing phosphorus-substituted quaternary carbon centers in high yields(up to 98%yield)within merely 5min.This environmentally benign protocol represents a unique example of 1,6-conjugate additions of propargylic p-QMs and aza-p-QMs for site-selective C-P bond formation in an operationally simple and atom-economical manner.The use of readily available Brønsted acid catalyst,operationally simplicity,high yields,and high atom economy make this protocol very facile,practical,easily scaled-up and environmentally friendly.展开更多
P-chiral organophosphorus compounds have demonstrated unparalleled application potential in diverse fields,including medicine,agricultural science,material science,and life science.Furthermore,they serve as highly eff...P-chiral organophosphorus compounds have demonstrated unparalleled application potential in diverse fields,including medicine,agricultural science,material science,and life science.Furthermore,they serve as highly effective chiral ligands in both transition metal-catalyzed and organocatalytic asymmetric transformations.In recent years,significant advances have been made in the catalytic asymmetric synthesis of P-chiral organophosphorus compounds,with asymmetric phosphination and hydrophosphination reactions emerging as the dominant strategies.This review systematically summarizes the methodological developments from 2020 to present for constructing P-chiral organophosphorus compounds.The discussion is organized according to different transition metals,aiming to provide a valuable reference and inspiration for researchers in organic synthesis and organophosphorus chemistry.展开更多
文摘For this work, we have selected two reactions for the formation of (2,2)-dichloro (ethyl) Arylphosphine and bis (2,2)-dichloro(ethyl)arylphosphine compounds by hydrophosphination. Global and local reactivity parameters, thermodynamic parameters of reactions, Transition states, the Fukui function, the local softness, the local electrophility index, and nucleophility index, Natural population analyses (NPA) and Mulliken (MK) were calculated with DFT method at B3LYP/6-311+G(d, p) level. The analysis of potential energy surfaces and the nature of the reaction mechanism have been determined. The various results obtained revealed that the addition of Arylphosphine is regiospecific. The phenylphosphine is more stable than the thiophenylphosphine. The theoretical results are consistent with experience.
基金We are grateful for financial support from the National Natural Science Foundation of China(No.21762005)Natural Science Foundation of Guangxi Province(No.2021GXNSFDA075005).
文摘An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addition under ultrasonic irradiation is described.This methodology provides a rapid and green approach for the construction of diarylmethyl phosphorus oxides bearing phosphorus-substituted quaternary carbon centers in high yields(up to 98%yield)within merely 5min.This environmentally benign protocol represents a unique example of 1,6-conjugate additions of propargylic p-QMs and aza-p-QMs for site-selective C-P bond formation in an operationally simple and atom-economical manner.The use of readily available Brønsted acid catalyst,operationally simplicity,high yields,and high atom economy make this protocol very facile,practical,easily scaled-up and environmentally friendly.
基金support from the National Natural Science Foundation of China(Nos.22377097,22074114)the Natural Science Foundation of Hubei Province(No.2024AFB233)+3 种基金the Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)the Science Research Foundation of Hubei Provincial Department of Education(No.Q20221513)the Postdoctoral Innovation Talent Program of Hubei Province(No.2024HBBHCXB074)the Science Foundation of Wuhan Institute of Technology(No.K2023116).
文摘P-chiral organophosphorus compounds have demonstrated unparalleled application potential in diverse fields,including medicine,agricultural science,material science,and life science.Furthermore,they serve as highly effective chiral ligands in both transition metal-catalyzed and organocatalytic asymmetric transformations.In recent years,significant advances have been made in the catalytic asymmetric synthesis of P-chiral organophosphorus compounds,with asymmetric phosphination and hydrophosphination reactions emerging as the dominant strategies.This review systematically summarizes the methodological developments from 2020 to present for constructing P-chiral organophosphorus compounds.The discussion is organized according to different transition metals,aiming to provide a valuable reference and inspiration for researchers in organic synthesis and organophosphorus chemistry.
