5,6-Dihydrothieno[3＇,2＇：4,5]thieno[2,3-d]pyrimidin-4（3H）-ones 6 were synthesized in yields of 71-87% by a consecutive method, which includes aza-Wittig reaction of iminophosphorane 3 with aromatic isocynate to gi...5,6-Dihydrothieno[3＇,2＇：4,5]thieno[2,3-d]pyrimidin-4（3H）-ones 6 were synthesized in yields of 71-87% by a consecutive method, which includes aza-Wittig reaction of iminophosphorane 3 with aromatic isocynate to give carbodiimide 4 and subsequent reaction of 4 with various amines, phenols or alcohols in the presence of catalytic amount of sodium ethoxide or solid potassium carbonate. 2009 Ming Wu Ding. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates a...A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates and amines produced 2,5,6-trisubstituted oxazolo[5,4-d]pyrimidi-7（6H）-ones 7 in good overall yields in the presence of catalytic amount of EtONa.展开更多
α,β-Alkynyl ketoesters were introduced to the enantioselective Henry reaction(nitroaldol condensation)with nitromethane catalyzed by tartaric acid derived chiral iminophosphoranes.As such,a variety of optically act...α,β-Alkynyl ketoesters were introduced to the enantioselective Henry reaction(nitroaldol condensation)with nitromethane catalyzed by tartaric acid derived chiral iminophosphoranes.As such,a variety of optically activeβ-nitro-substituted tertiary alcohols bearing alkyne moieties were obtained in good to excellent yields(42%–99%)and moderate to good level of enantiomeric excess(up to 87%ee).展开更多
A series of coordination gold(Ⅲ),palladium(Ⅱ),and platinum(Ⅱ)complexes with a luminescent iminophosphorane ligand derived from 8-aminoquinoline[Ph_(3)PvN-C_(9)H_(6)N](1)have been synthesized and structurally charac...A series of coordination gold(Ⅲ),palladium(Ⅱ),and platinum(Ⅱ)complexes with a luminescent iminophosphorane ligand derived from 8-aminoquinoline[Ph_(3)PvN-C_(9)H_(6)N](1)have been synthesized and structurally characterized.The coordination palladium(Ⅱ)and platinum(Ⅱ)compounds can evolve further,under appropriate conditions,to give stable cyclometalated endo species[M{κ_(3)-C,N,N-C_(6)H_(4)(PPh_(2)vN-8-C_(9)H_(6)N)}Cl](M=Pd,Pt)by C-H activation of the phenyl group of the PPh_(3)fragment.展开更多
An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(DME)](X=Cl,Br).The corresponding complexes(2X,X=Cl,Br)were isolated and characterised among others by multinuclear NMR spectroscopy an...An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(DME)](X=Cl,Br).The corresponding complexes(2X,X=Cl,Br)were isolated and characterised among others by multinuclear NMR spectroscopy and X-ray crystallography.The collected data suggest that different geometries coexist in solution at room temperature.2Cl proved to be an efficient hydrosilylation catalyst able to perform at a loading of 1 mol%in the presence of one equivalent of SiH_(2)Ph_(2) and 1 mol%of tBuOK,with the reduction of C=C and C=O bonds in high yield in 1 h for most substrates.Moreover,the selective conversion of the C=O bond to a silylether linkage was observed for nine enones.Therefore,2Cl presents a rather unique catalytic behaviour compared to previously described Ni catalysts.Both experimental and theoretical investigations regarding the mechanism suggest the involvement of a Ni-H complex.The computed mechanism presents a highest-lying transition state at only 19.0 kcal mol^(-1) and shows that the reaction is driven by favorable thermodynamics.展开更多
Heteroleptic stannylenes,featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands,were synthesized straightforwardly through formal C-H activation.Subsequently,they w...Heteroleptic stannylenes,featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands,were synthesized straightforwardly through formal C-H activation.Subsequently,they were investigated for their ability to activate ammonia through N-H bond scission.By combining synthetic modifications of the ancillary ligand framework and computational analyses,detailed insights into the mechanism of NH_(3) activation by these systems were obtained,highlighting an activation pathway at tin without a change in oxidation state.Additionally,an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials,providing access to a novel lithium stannylenoid.展开更多
The carbodiimide 2,obtained from the aza-Wittig reactions of iminophosphorane 1 with alkyl isocyanates,reacted with primary amino to give 2-alkylamino benzo[b]thieno[3,2-d]pyrimidin-4(3H)-ones 4 and 5.The formation me...The carbodiimide 2,obtained from the aza-Wittig reactions of iminophosphorane 1 with alkyl isocyanates,reacted with primary amino to give 2-alkylamino benzo[b]thieno[3,2-d]pyrimidin-4(3H)-ones 4 and 5.The formation mechanism of the title compounds has been investigated.展开更多
Novel 2-aryloxy-5-(2-furfurylidene)-4H-imidazolin-4-ones 6 were synthesized by aza-Wittig reaction of vinyliminophosphorane 4 with phenyl isocyanate and subsequent condensation with Various substituted phenols in the ...Novel 2-aryloxy-5-(2-furfurylidene)-4H-imidazolin-4-ones 6 were synthesized by aza-Wittig reaction of vinyliminophosphorane 4 with phenyl isocyanate and subsequent condensation with Various substituted phenols in the presence of catalytic amount of potassium carbonate. The products are confirmed by H-1 NMR, MS, IR and elementary analysis.展开更多
Dialkylamino-4(3H)-quinazolinones 4 were rapidly synthesized by a solution-phase parallel synthetic method, which includes aza-Wittig reaction of iminophosphorane 1 with aromatic isocynate to give carbodiimide 2 and s...Dialkylamino-4(3H)-quinazolinones 4 were rapidly synthesized by a solution-phase parallel synthetic method, which includes aza-Wittig reaction of iminophosphorane 1 with aromatic isocynate to give carbodiimide 2 and subsequent reaction of 2 with various aliphatic secondary amine in a parallel fashion.展开更多
4（3H）-Quinazolinones have been synthesized from poly（ethylene glycol） （PEG） supported aza-Wittig reaction. 2-Dialkylamino- 4（3H）-quinazolinones 6 were synthesized efficiently by reaction of secondary amine wit...4（3H）-Quinazolinones have been synthesized from poly（ethylene glycol） （PEG） supported aza-Wittig reaction. 2-Dialkylamino- 4（3H）-quinazolinones 6 were synthesized efficiently by reaction of secondary amine with PEG-supported carbodiimides 4, which were obtained from aza-Wittig reaction of PEG-supported iminophosphoranes 3 with isocyanates.展开更多
Alkylamino-5, 6, 7, 8-tetrahydrobenzothieno [2, 3-d] pyrimidin-4(3H)-ones 7 weresynthesized by a new selective synthetic method, which includes aza-Wittig reaction of imino-phosphorane 4 with aromatic isocynate to giv...Alkylamino-5, 6, 7, 8-tetrahydrobenzothieno [2, 3-d] pyrimidin-4(3H)-ones 7 weresynthesized by a new selective synthetic method, which includes aza-Wittig reaction of imino-phosphorane 4 with aromatic isocynate to give carbodiimide 5 and subsequent reaction of 5 withvarious aliphatic primary amine in the presence of EtO-Na+.展开更多
Chiral organobases occupy a significant position in asymmetric organocatalysis. The general types of chiral organobases include tertiary amines, amidines, guanidines, cyclopropenimines, and iminophosphoranes, etc. The...Chiral organobases occupy a significant position in asymmetric organocatalysis. The general types of chiral organobases include tertiary amines, amidines, guanidines, cyclopropenimines, and iminophosphoranes, etc. These organobases are demonstrated to be effective organocatalysts to promote divers kinds of base-initiated reactions in excellent yields and stereoselectivities. In previous reports, several groups have summarized each kind of chiral organobases in different reviews. To the aim of understanding the whole of them in one review, herein, we provide a brief introduction of these chiral organobases in asymmetric catalysis.展开更多
The title compound 2-（4＇-methylphenoxy）-5,8,9-trimethyl-3-phenyl thieno[3＇,2＇：5,6] pyrido[4,3-d]pyrimidin-4（3H）-one hydrochloride （C26H23Cl4N3O2S, Mr = 583.33） has been determined by single-crystal X-ray dif...The title compound 2-（4＇-methylphenoxy）-5,8,9-trimethyl-3-phenyl thieno[3＇,2＇：5,6] pyrido[4,3-d]pyrimidin-4（3H）-one hydrochloride （C26H23Cl4N3O2S, Mr = 583.33） has been determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.8442（ 11 ）, b = 11.5131 （8）, c = 17.2010（13） A, β = 113.7250（10）°, V = 2691.3（3） ,A^3, Z = 4, Dc = 1.440 g/cm^3, S = 1.094,μ = 0.547 mm^-1, F（000） = 1200, the final R = 0.0571 and wR = 0.1458. X-ray analysis reveals that the title compound combines with a molecule of dichloromethane by an intramolecular hydrogen bond. The thienopyridine ring is almost coplanar, and the dihedral angle between the thiophene plane and the pyridine plane is 0.6°.展开更多
Reaction<span style="font-family:""><span style="font-family:Verdana;"> of ethyl (Z)-3-(heteroaryl/aryl)-2-((triphenyl-<span style="font-family:Verdana;">λ<sup&...Reaction<span style="font-family:""><span style="font-family:Verdana;"> of ethyl (Z)-3-(heteroaryl/aryl)-2-((triphenyl-<span style="font-family:Verdana;">λ<sup><span style="font-family:Verdana;">5</sup><span style="font-family:Verdana;">-phosphaneylidene) amino) acrylates intermediates with 2,3-thiophenedicarboxaldehyde w<span style="font-family:Verdana;">as<span style="font-family:Verdana;"> used<span style="font-family:Verdana;"> in novel Tandem three consecutive reactions: aza-Wittig, imine condensation and electrophilic heteroaromatic cyclization to obtain a series of indolizines. A tentative mechanism of this reaction is proposed.展开更多
In the presence of Cu（I） and triethyl amine, one-pot three-component reaction of fluoroalkanesulfonyl azides, alkynes and iminophosphoranes in CH2Cl2 at room temperature gave a novel class of fluorinated phosphorus ...In the presence of Cu（I） and triethyl amine, one-pot three-component reaction of fluoroalkanesulfonyl azides, alkynes and iminophosphoranes in CH2Cl2 at room temperature gave a novel class of fluorinated phosphorus amidines in good yields.展开更多
3-Iodoindole N-carboximidamides and N-carboximidoates 4 were prepared regioselectively via a sequential aza-Wittig/iodine induced cyclization, starting from easily accessible 2-alkynylphenyl iminophosphorane, isocyana...3-Iodoindole N-carboximidamides and N-carboximidoates 4 were prepared regioselectively via a sequential aza-Wittig/iodine induced cyclization, starting from easily accessible 2-alkynylphenyl iminophosphorane, isocyanates, various nucleophiles and iodine.展开更多
基金support of this work by the National Natural Science Foundation of China(No.20772041)Key Project of Science and Technology of Ministry of Education of China(No.107082)
文摘5,6-Dihydrothieno[3＇,2＇：4,5]thieno[2,3-d]pyrimidin-4（3H）-ones 6 were synthesized in yields of 71-87% by a consecutive method, which includes aza-Wittig reaction of iminophosphorane 3 with aromatic isocynate to give carbodiimide 4 and subsequent reaction of 4 with various amines, phenols or alcohols in the presence of catalytic amount of sodium ethoxide or solid potassium carbonate. 2009 Ming Wu Ding. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金financial support of this work by the National Natural Science Foundation of China(No.21172085)the Natural Science Foundation of Hubei Province(No. 2014CFB567)the Open Foundation of Hubei Province Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients
文摘A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates and amines produced 2,5,6-trisubstituted oxazolo[5,4-d]pyrimidi-7（6H）-ones 7 in good overall yields in the presence of catalytic amount of EtONa.
基金supported by grants from National Key Program(No.2016YFA0200302,Study on application and preparation of aroma nanocomposites)National Natural Science Foundation of China(NSFC,No.21472213)Croucher Foundation(Hong Kong)in the form of a CAS-Croucher Foundation Joint Laboratory Grant
文摘α,β-Alkynyl ketoesters were introduced to the enantioselective Henry reaction(nitroaldol condensation)with nitromethane catalyzed by tartaric acid derived chiral iminophosphoranes.As such,a variety of optically activeβ-nitro-substituted tertiary alcohols bearing alkyne moieties were obtained in good to excellent yields(42%–99%)and moderate to good level of enantiomeric excess(up to 87%ee).
基金Research at Brooklyn College was supported by a grant from the National Institute of General Medical Sciences(NIGMS),SC2GM082307a grant from the National Cancer Institute(NCI),1SC1CA182844(M.C.)+1 种基金the MINECO“Ministerio de Ciencia y Economía”(CTQ2011-22589)Gobierno de Aragón(Dpto.de Ciencia,Tecnología y Universidad)for financial support(J.J.).
文摘A series of coordination gold(Ⅲ),palladium(Ⅱ),and platinum(Ⅱ)complexes with a luminescent iminophosphorane ligand derived from 8-aminoquinoline[Ph_(3)PvN-C_(9)H_(6)N](1)have been synthesized and structurally characterized.The coordination palladium(Ⅱ)and platinum(Ⅱ)compounds can evolve further,under appropriate conditions,to give stable cyclometalated endo species[M{κ_(3)-C,N,N-C_(6)H_(4)(PPh_(2)vN-8-C_(9)H_(6)N)}Cl](M=Pd,Pt)by C-H activation of the phenyl group of the PPh_(3)fragment.
基金granted access to the HPC resources of CINES under allocation 2020-A0070810977 made by GENCI to VGThe Agence Nationale de la Recherche(ANR-21-CE07-0026)is acknowledged for funding the LYMACATO project,and the RESOMAG platform for access to NMR instruments,as well as GDR Phosphore for gathering the community of P-chemists in France.
文摘An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(DME)](X=Cl,Br).The corresponding complexes(2X,X=Cl,Br)were isolated and characterised among others by multinuclear NMR spectroscopy and X-ray crystallography.The collected data suggest that different geometries coexist in solution at room temperature.2Cl proved to be an efficient hydrosilylation catalyst able to perform at a loading of 1 mol%in the presence of one equivalent of SiH_(2)Ph_(2) and 1 mol%of tBuOK,with the reduction of C=C and C=O bonds in high yield in 1 h for most substrates.Moreover,the selective conversion of the C=O bond to a silylether linkage was observed for nine enones.Therefore,2Cl presents a rather unique catalytic behaviour compared to previously described Ni catalysts.Both experimental and theoretical investigations regarding the mechanism suggest the involvement of a Ni-H complex.The computed mechanism presents a highest-lying transition state at only 19.0 kcal mol^(-1) and shows that the reaction is driven by favorable thermodynamics.
文摘Heteroleptic stannylenes,featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands,were synthesized straightforwardly through formal C-H activation.Subsequently,they were investigated for their ability to activate ammonia through N-H bond scission.By combining synthetic modifications of the ancillary ligand framework and computational analyses,detailed insights into the mechanism of NH_(3) activation by these systems were obtained,highlighting an activation pathway at tin without a change in oxidation state.Additionally,an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials,providing access to a novel lithium stannylenoid.
基金supported by Huazhong Agricultural University Scientific&Technological Self-innovation Foundation(Nos.2007XRC064 and 2008XKJC005)
文摘The carbodiimide 2,obtained from the aza-Wittig reactions of iminophosphorane 1 with alkyl isocyanates,reacted with primary amino to give 2-alkylamino benzo[b]thieno[3,2-d]pyrimidin-4(3H)-ones 4 and 5.The formation mechanism of the title compounds has been investigated.
基金the National Natural Science Foundation of China(Project No.20102001).
文摘Novel 2-aryloxy-5-(2-furfurylidene)-4H-imidazolin-4-ones 6 were synthesized by aza-Wittig reaction of vinyliminophosphorane 4 with phenyl isocyanate and subsequent condensation with Various substituted phenols in the presence of catalytic amount of potassium carbonate. The products are confirmed by H-1 NMR, MS, IR and elementary analysis.
文摘Dialkylamino-4(3H)-quinazolinones 4 were rapidly synthesized by a solution-phase parallel synthetic method, which includes aza-Wittig reaction of iminophosphorane 1 with aromatic isocynate to give carbodiimide 2 and subsequent reaction of 2 with various aliphatic secondary amine in a parallel fashion.
基金We gratefully acknowledge financial support of this work by the Natural Science Foundation of Hubei Province （No. 2006ABB016） the National Natural Science Foundation of China （No. 20772041） Key Project of Chinese Ministry of Education （No. 107082）.
文摘4（3H）-Quinazolinones have been synthesized from poly（ethylene glycol） （PEG） supported aza-Wittig reaction. 2-Dialkylamino- 4（3H）-quinazolinones 6 were synthesized efficiently by reaction of secondary amine with PEG-supported carbodiimides 4, which were obtained from aza-Wittig reaction of PEG-supported iminophosphoranes 3 with isocyanates.
基金We gratefully acknowledge financial support of this work by the National Key Project for Basic Research(2003CB114400,2003CB114406)the National Natural Science Foundation of China(Project No.20102001).
文摘Alkylamino-5, 6, 7, 8-tetrahydrobenzothieno [2, 3-d] pyrimidin-4(3H)-ones 7 weresynthesized by a new selective synthetic method, which includes aza-Wittig reaction of imino-phosphorane 4 with aromatic isocynate to give carbodiimide 5 and subsequent reaction of 5 withvarious aliphatic primary amine in the presence of EtO-Na+.
基金the National Natural Science Foundation of China (Nos. 21625205 and 21332003)the National Program for Support of Top-Notch Young Professionals for financial support
文摘Chiral organobases occupy a significant position in asymmetric organocatalysis. The general types of chiral organobases include tertiary amines, amidines, guanidines, cyclopropenimines, and iminophosphoranes, etc. These organobases are demonstrated to be effective organocatalysts to promote divers kinds of base-initiated reactions in excellent yields and stereoselectivities. In previous reports, several groups have summarized each kind of chiral organobases in different reviews. To the aim of understanding the whole of them in one review, herein, we provide a brief introduction of these chiral organobases in asymmetric catalysis.
基金This work was financially supported by the National Key Project for Basic Research (No. 2003CB114400) and the National Natural Science Foundation of China (No. 20372023).
文摘The title compound 2-（4＇-methylphenoxy）-5,8,9-trimethyl-3-phenyl thieno[3＇,2＇：5,6] pyrido[4,3-d]pyrimidin-4（3H）-one hydrochloride （C26H23Cl4N3O2S, Mr = 583.33） has been determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.8442（ 11 ）, b = 11.5131 （8）, c = 17.2010（13） A, β = 113.7250（10）°, V = 2691.3（3） ,A^3, Z = 4, Dc = 1.440 g/cm^3, S = 1.094,μ = 0.547 mm^-1, F（000） = 1200, the final R = 0.0571 and wR = 0.1458. X-ray analysis reveals that the title compound combines with a molecule of dichloromethane by an intramolecular hydrogen bond. The thienopyridine ring is almost coplanar, and the dihedral angle between the thiophene plane and the pyridine plane is 0.6°.
文摘Reaction<span style="font-family:""><span style="font-family:Verdana;"> of ethyl (Z)-3-(heteroaryl/aryl)-2-((triphenyl-<span style="font-family:Verdana;">λ<sup><span style="font-family:Verdana;">5</sup><span style="font-family:Verdana;">-phosphaneylidene) amino) acrylates intermediates with 2,3-thiophenedicarboxaldehyde w<span style="font-family:Verdana;">as<span style="font-family:Verdana;"> used<span style="font-family:Verdana;"> in novel Tandem three consecutive reactions: aza-Wittig, imine condensation and electrophilic heteroaromatic cyclization to obtain a series of indolizines. A tentative mechanism of this reaction is proposed.
基金Project supported by the National Natural Science Foundation of China （Nos. 21032006, 20972178） and Shanghai Natural Science Council.
文摘In the presence of Cu（I） and triethyl amine, one-pot three-component reaction of fluoroalkanesulfonyl azides, alkynes and iminophosphoranes in CH2Cl2 at room temperature gave a novel class of fluorinated phosphorus amidines in good yields.
文摘3-Iodoindole N-carboximidamides and N-carboximidoates 4 were prepared regioselectively via a sequential aza-Wittig/iodine induced cyclization, starting from easily accessible 2-alkynylphenyl iminophosphorane, isocyanates, various nucleophiles and iodine.
