Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.
The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained i...The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.展开更多
A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the pres...A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the present protocol attractive.展开更多
1-(β-Hydroxyalkyl)-1,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-1,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
The substitution reaction between gem-diacetates and allylsamarium bromide was investigated, and homoallylic alcohol acetates were obtained in moderate to good yields.
Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides f...Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.展开更多
The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to hig...The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to high chemical yields and moderate enantioselectivities were obtained.展开更多
The reaction of diethyl malonate with various substituted 1,2-allenic ketone can be catalyzed by 10% of K2CO3leading to polyfunctionalized β, γ-unsaturated enones 3 or 4. With 3-unsaturated 1-substituted-1, 2-al... The reaction of diethyl malonate with various substituted 1,2-allenic ketone can be catalyzed by 10% of K2CO3leading to polyfunctionalized β, γ-unsaturated enones 3 or 4. With 3-unsaturated 1-substituted-1, 2-allenic ketones, the highly selective formation of β, γ-unsaturated enones 4 was observed; with 1,2-allenic ketones with one or two γ-substituents, only β, γ-unsaturated enones 3 with an unmigrated carbon-carbon double bond were produced; with γ-monosubstituted-1,2-allenic ketones the corresponding (E)-3 were formed highly selectively; with propadienyl ketones, a mixture of β, γ-unsaturated enones 3 and 4 were formed.……展开更多
The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3)...The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.展开更多
A series of 2,4-dibromobutenes were synthesized by the reaction of methylenecyclopropanes with KBr in HOAc in the presence of dibenzoyl peroxide, providing an environment friendly method for the synthesis of 2,4-dibro...A series of 2,4-dibromobutenes were synthesized by the reaction of methylenecyclopropanes with KBr in HOAc in the presence of dibenzoyl peroxide, providing an environment friendly method for the synthesis of 2,4-dibromobutenes.展开更多
The crystal and molecular structures of (E,E)-1,10-bis-(4-fluorophenyl)-3,8-dime- thyl-deca-3,7-diene-1,10-dione have been determined by X-ray diffraction method. The crystal (C24- H24F2O2, Mr = 382.45) is of monoclin...The crystal and molecular structures of (E,E)-1,10-bis-(4-fluorophenyl)-3,8-dime- thyl-deca-3,7-diene-1,10-dione have been determined by X-ray diffraction method. The crystal (C24- H24F2O2, Mr = 382.45) is of monoclinic, space group P21/c, a = 11.0392(5), b = 11.3620(4), c = 7.9361(3) ?, β = 97.423(2)o, V = 987.06(7) ?3, Z = 2, Dc = 1.287 g/cm3, μ(Mo-Kα) = 0.93 cm-1, λ = 0.7107 ?, F(000) = 404.00, the final R = 0.0530 and wR = 0.150 for 1348 observed reflections (I > 2σ(I)). X-ray analysis revealed that there exists a double bond in C(9)–C(11) with the bond length of 1.324(3) ?, while the C(8)–C(9) bond length is 1.508(3) ? and it may be assigned to a single bond. These results show that the C=C bond is not conjugated with the C=O bond.展开更多
In the presence of metallic samariumcobalt (II) chloride hexahydrate, the nitrones can be reduced to the corresponding imines in moderate to high yields under mild and neutral conditions.
The title compound {(5:(1-[(2-MeOC6H4)C3H6]C9H6}Li(DME) (DME = 1,2-di- methoxy-ethylene) was synthesized by the treatment of 3-[(2-methoxyphenyl)-isopropyl]-indene with 1 equiv. of n-BuLi followed by the recrystalliza...The title compound {(5:(1-[(2-MeOC6H4)C3H6]C9H6}Li(DME) (DME = 1,2-di- methoxy-ethylene) was synthesized by the treatment of 3-[(2-methoxyphenyl)-isopropyl]-indene with 1 equiv. of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a = 14.5677(3), b = 15.54670(10), c = 18.7498(3) , Z = 8, V = 4246.45(11) 3, Dc = 1.127 g/cm3 and ((MoK() = 0.072 mm-1. The coordination geometry can be described as a distorted tetrahedron.展开更多
5-Hydroxyfuran-2(5H)ones are an important class of compounds because they often occur in natural products and exhibit a broad range of biological activities. Recently, much attention has been focused on the effici... 5-Hydroxyfuran-2(5H)ones are an important class of compounds because they often occur in natural products and exhibit a broad range of biological activities. Recently, much attention has been focused on the efficient and di verse synthesis of these compounds, particularly 4-halo-5-hydroxy-2(5H)-furanones. The typical synthetic strategies include acid catalyzed cyclization of ketonic acids, auto oxidation of corresponding lactone in air, rearrangement reactions of α-phenylsulphinylacrylates, oxidation with chromium trioxide in acetic acid, and bromination-hydrolysis of α ,β-butanolides. Herein, we wish to report that 4-halo-5-hydroxyfuran-2(5H)-ones were synthesized via the efficient sequential halolactonization-hydroxylation reaction of 4-aryl-2,3-allenoic acids with I2 or CuX2 (X = Br or Cl) inmoderate to good yields.……展开更多
Allenes are three carbon functional groups possessing two perpendicular π-orbitals. Their unique reaction be havior is spread over three carbon atoms, which shows great potential in organic synthesis in terms of ... Allenes are three carbon functional groups possessing two perpendicular π-orbitals. Their unique reaction be havior is spread over three carbon atoms, which shows great potential in organic synthesis in terms of chirality transfer and diversity, as a result of the axial chirality as well as the substituent-loading capability. Recently, we devoted ourselves to establish a new area of oxidative cyclization-dimerization reactions between two functionalized allenes to give interesting bicyclic compounds in a single step. The formidable challenges are to match the reactivities of two allenes, and regenerate the catalyst, which would be reduced after reductive-elimination. In this paper we wish to disclose our recent studies on the synthesis of bi-butenolides from oxidative cyclization self-coupling reaction of 2,3 allenoic acids, in which a new system (PdCl2/RI/air) for regeneration of the palladium(Ⅱ) species was observed.……展开更多
Organoboronic acids enjoy high prestige in the metal-catalyzed C-C bond formations. The most notable progress is the rhodium- and nickel-catalyzed conjugate addition with unsaturated carbon-carbon bond, aldehydes,... Organoboronic acids enjoy high prestige in the metal-catalyzed C-C bond formations. The most notable progress is the rhodium- and nickel-catalyzed conjugate addition with unsaturated carbon-carbon bond, aldehydes, N-sulfonyl imines reported by Miyaura, Hayashi and Shirakawa.[1]……展开更多
基金the National Natural Science Foundation of China(Project No.20072033)Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.
文摘The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.
基金the National Natural Science Foundation of China (No. 20072033)Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the present protocol attractive.
基金the National Natural Science Foundation of China(Project No.20072033)the NSF of Zhejiang Province for financial support.
文摘1-(β-Hydroxyalkyl)-1,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-1,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
文摘The substitution reaction between gem-diacetates and allylsamarium bromide was investigated, and homoallylic alcohol acetates were obtained in moderate to good yields.
基金Project (No. 20072033) supported by the National Natural ScienceFoundation of China and Specialized Research Fund for the DoctoralProgram of Higher Education of China
文摘Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.
基金National Natural Science Foundation of China(No.20102002,20472028)Science Foundation of Jiangsu Province for their financial support(No.20332050).
文摘The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to high chemical yields and moderate enantioselectivities were obtained.
基金Project supported by the National Natural Science Foundation of China, the Major State Basic Research Development Program (No. G2000077500), and Hong Kong Qiu Shi Foundation of Science and Technology (1999 ~ 2003).
文摘 The reaction of diethyl malonate with various substituted 1,2-allenic ketone can be catalyzed by 10% of K2CO3leading to polyfunctionalized β, γ-unsaturated enones 3 or 4. With 3-unsaturated 1-substituted-1, 2-allenic ketones, the highly selective formation of β, γ-unsaturated enones 4 was observed; with 1,2-allenic ketones with one or two γ-substituents, only β, γ-unsaturated enones 3 with an unmigrated carbon-carbon double bond were produced; with γ-monosubstituted-1,2-allenic ketones the corresponding (E)-3 were formed highly selectively; with propadienyl ketones, a mixture of β, γ-unsaturated enones 3 and 4 were formed.……
基金The project was supported by the NNSFC (No. 20525101)the NSF of Jiangsu Province (No. BK2004205)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20050285004)the State Key Laboratory of Organometallic Chemistry (No. 06-26)
文摘The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.
文摘A series of 2,4-dibromobutenes were synthesized by the reaction of methylenecyclopropanes with KBr in HOAc in the presence of dibenzoyl peroxide, providing an environment friendly method for the synthesis of 2,4-dibromobutenes.
基金This work was supported by the National Natural Science Foundation of China (No. 20072033) Specialized Research Fund for the Doctoral Program of Higher Education of China
文摘The crystal and molecular structures of (E,E)-1,10-bis-(4-fluorophenyl)-3,8-dime- thyl-deca-3,7-diene-1,10-dione have been determined by X-ray diffraction method. The crystal (C24- H24F2O2, Mr = 382.45) is of monoclinic, space group P21/c, a = 11.0392(5), b = 11.3620(4), c = 7.9361(3) ?, β = 97.423(2)o, V = 987.06(7) ?3, Z = 2, Dc = 1.287 g/cm3, μ(Mo-Kα) = 0.93 cm-1, λ = 0.7107 ?, F(000) = 404.00, the final R = 0.0530 and wR = 0.150 for 1348 observed reflections (I > 2σ(I)). X-ray analysis revealed that there exists a double bond in C(9)–C(11) with the bond length of 1.324(3) ?, while the C(8)–C(9) bond length is 1.508(3) ? and it may be assigned to a single bond. These results show that the C=C bond is not conjugated with the C=O bond.
文摘In the presence of metallic samariumcobalt (II) chloride hexahydrate, the nitrones can be reduced to the corresponding imines in moderate to high yields under mild and neutral conditions.
基金This work was supported by the National Natural Science Foundation of China (No. 20472001), the program for NCET (NCET-04-590), and the Excellent Young Scholars foundation of Anhui Province (04046079) and a grant from Anhui Education Department (2005hbz06)
文摘The title compound {(5:(1-[(2-MeOC6H4)C3H6]C9H6}Li(DME) (DME = 1,2-di- methoxy-ethylene) was synthesized by the treatment of 3-[(2-methoxyphenyl)-isopropyl]-indene with 1 equiv. of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a = 14.5677(3), b = 15.54670(10), c = 18.7498(3) , Z = 8, V = 4246.45(11) 3, Dc = 1.127 g/cm3 and ((MoK() = 0.072 mm-1. The coordination geometry can be described as a distorted tetrahedron.
基金Project supported by the National Natural Science Foundation of China, the Major State Basic Research Development Program (No. G2000077500), and Hong Kong Qiu Shi Foundation of Science and Technology (1999 ~ 2003).
文摘 5-Hydroxyfuran-2(5H)ones are an important class of compounds because they often occur in natural products and exhibit a broad range of biological activities. Recently, much attention has been focused on the efficient and di verse synthesis of these compounds, particularly 4-halo-5-hydroxy-2(5H)-furanones. The typical synthetic strategies include acid catalyzed cyclization of ketonic acids, auto oxidation of corresponding lactone in air, rearrangement reactions of α-phenylsulphinylacrylates, oxidation with chromium trioxide in acetic acid, and bromination-hydrolysis of α ,β-butanolides. Herein, we wish to report that 4-halo-5-hydroxyfuran-2(5H)-ones were synthesized via the efficient sequential halolactonization-hydroxylation reaction of 4-aryl-2,3-allenoic acids with I2 or CuX2 (X = Br or Cl) inmoderate to good yields.……
基金Project supported by the Major State Basic Research Development Program (No. G2000077500), the National Natural Science Foundation of China (No. 20172060), and Hong Kong Qiu Shi Foundation of Science and Technology (1999 ~ 2003).
文摘 Bicyclic alkaloids having izidine skeletons, are widely observed in various plant families, which show tumor inhibitory activity.……
基金Project supported by the National Natural Science Foundation of China, the Major State Basic Research Development Program (No. G2000077500), and Hong Kong Qiu Shi Foundation of Science and Technology (1999 ~ 2003).
文摘 Allenes are three carbon functional groups possessing two perpendicular π-orbitals. Their unique reaction be havior is spread over three carbon atoms, which shows great potential in organic synthesis in terms of chirality transfer and diversity, as a result of the axial chirality as well as the substituent-loading capability. Recently, we devoted ourselves to establish a new area of oxidative cyclization-dimerization reactions between two functionalized allenes to give interesting bicyclic compounds in a single step. The formidable challenges are to match the reactivities of two allenes, and regenerate the catalyst, which would be reduced after reductive-elimination. In this paper we wish to disclose our recent studies on the synthesis of bi-butenolides from oxidative cyclization self-coupling reaction of 2,3 allenoic acids, in which a new system (PdCl2/RI/air) for regeneration of the palladium(Ⅱ) species was observed.……
基金Project supported by the Major State Basic Research Development Program (No. G2000077500), the National Natural Science Foundation of Chi na, Shanghai Municipal Committee of Science and Technology, and Hong Kong Qiu Shi Foundation of Science and Technolog(1999~2003)
文摘 Organoboronic acids enjoy high prestige in the metal-catalyzed C-C bond formations. The most notable progress is the rhodium- and nickel-catalyzed conjugate addition with unsaturated carbon-carbon bond, aldehydes, N-sulfonyl imines reported by Miyaura, Hayashi and Shirakawa.[1]……