含磷吲哚衍生物是一类重要的有机磷化合物,不仅广泛存在于医药制剂中,而且作为配体和中间体广泛存在于材料学和有机合成中。利用膦亲核试剂对磺酰吲哚原位生成的插烯亚胺中间体进行迈克尔加成,能够以较高收率得到一系列3-膦取代吲哚化...含磷吲哚衍生物是一类重要的有机磷化合物,不仅广泛存在于医药制剂中,而且作为配体和中间体广泛存在于材料学和有机合成中。利用膦亲核试剂对磺酰吲哚原位生成的插烯亚胺中间体进行迈克尔加成,能够以较高收率得到一系列3-膦取代吲哚化合物。以磺酰基吲哚和二苯基氧磷为原料,在无机碱碳酸铯作用下发生迈克尔加成反应,合成了11个结构新颖的3-(1-磷酰基)甲基吲哚类化合物3a~3k,产率为72%~98%,并对这些化合物进行^(1)H NMR、^(13)C NMR、31 P NMR、熔点和HR-MS(ESI-TOF)表征。展开更多
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
文摘含磷吲哚衍生物是一类重要的有机磷化合物,不仅广泛存在于医药制剂中,而且作为配体和中间体广泛存在于材料学和有机合成中。利用膦亲核试剂对磺酰吲哚原位生成的插烯亚胺中间体进行迈克尔加成,能够以较高收率得到一系列3-膦取代吲哚化合物。以磺酰基吲哚和二苯基氧磷为原料,在无机碱碳酸铯作用下发生迈克尔加成反应,合成了11个结构新颖的3-(1-磷酰基)甲基吲哚类化合物3a~3k,产率为72%~98%,并对这些化合物进行^(1)H NMR、^(13)C NMR、31 P NMR、熔点和HR-MS(ESI-TOF)表征。
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.
