The intermolecular coupling of a nitro group with a cyano group mediated by a Sm(Hg) amalgam prepared from metal samarium powder and catalytic mercury dichloride was studied.
The ? ?vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.
Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides wi...Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides with metallic zinc powder in aqueous media has been developed, which generates E-alkenes with excellent yields. The reactivity of vic-dibromides decreases in the order of 1,2-dibromo-1,2-diphenylethane>1,2-dibromo-1-phenylethane>1,2-dibromo-1,2-dialkylethane.展开更多
The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF),...The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.展开更多
Hydrozirconation of 1-alkylnylphosphonates gives the organozirconium(Ⅳ) complexes 2 in syn-addition way. Complexs 2 was trapped with NCS, NBS or I2 to afford stereodifined α-halo-1-alkenylphosphonates in moderate to...Hydrozirconation of 1-alkylnylphosphonates gives the organozirconium(Ⅳ) complexes 2 in syn-addition way. Complexs 2 was trapped with NCS, NBS or I2 to afford stereodifined α-halo-1-alkenylphosphonates in moderate to high yields.展开更多
The palladium catalyzed hydrostannation of 1-alkenylphosphonates gives the (E)-α-stannyl 1-alkenylphosphonates 2 stereospecifically. Compounds 2 can occur Stille coupling reaction to afford a, b-disubstituted vinylp...The palladium catalyzed hydrostannation of 1-alkenylphosphonates gives the (E)-α-stannyl 1-alkenylphosphonates 2 stereospecifically. Compounds 2 can occur Stille coupling reaction to afford a, b-disubstituted vinylphosphonates with the retention of the configuration.展开更多
Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) ...Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) to afford α,α'-bis(substituted benzylidene) cycloalkanones in good yields.展开更多
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselect...bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselectively reduced by Sm/HOAc system in an ionic liquid medium to afford aromatic amines. Under these conditions the other substituents, such as -X, -CHO, -COOH, -CN, -NHTos and -alkyl, remained intact. The notable advantages of this reaction are its mild conditions, simple operation, short reaction time, high yields and easy recycling of ionic liquid.展开更多
A general and practical procedure for the syntheses of 3,4 dihydropyrimidine 2(1 H ) thiones by a one pot condensation of aldehyde, β ketoester or β diketone and thiourea using La (OTf) 3 as the catalyst ...A general and practical procedure for the syntheses of 3,4 dihydropyrimidine 2(1 H ) thiones by a one pot condensation of aldehyde, β ketoester or β diketone and thiourea using La (OTf) 3 as the catalyst is described. Mild reaction conditions, excellent yields as well as the environmentally friendly character of La(OTf) 3 make it an important alternative to the classic acid catalyzed Biginelli's reaction.展开更多
Lanthanide compounds have been attracting much attention in organic synthesis. Chiral Ln substituted BINOL have been widely studied in several asymmetric organic reactions. LnCl 3 and Ln(OTf) 3 have been ex...Lanthanide compounds have been attracting much attention in organic synthesis. Chiral Ln substituted BINOL have been widely studied in several asymmetric organic reactions. LnCl 3 and Ln(OTf) 3 have been expected to serve as Lewis acids and have been applied to many important synthetic reactions in a one pot manner. Ln(O i Pr) 3 exhibits some basic characters, which also can be utilized in some special organic transformation. This article deals with some lanthanides(III) complexes promoted organic reactions, which we have recently developed.展开更多
A variety of lanthanocene complexes, e.g. chlorides, hydrocarbyls, amides, hydrides and divalent derivatives, were synthesized by using a series of designed cyclopentadienyl, indenyl and fluorenyl ligands with rin...A variety of lanthanocene complexes, e.g. chlorides, hydrocarbyls, amides, hydrides and divalent derivatives, were synthesized by using a series of designed cyclopentadienyl, indenyl and fluorenyl ligands with ring bridges or dornor functionalized sidearms. X Ray crystallographic analyses reveal the formation of intramolecular coordination bonds between central metals and heteroatoms (O, N) in sidearms or bridging chains. Some applications of these complexes are also discussed in this account.展开更多
基金National Natural Science Foundation of China (Project No. 20072033) and Natural Science Foundation of Zhejiang province for financial support.
文摘The intermolecular coupling of a nitro group with a cyano group mediated by a Sm(Hg) amalgam prepared from metal samarium powder and catalytic mercury dichloride was studied.
基金Project supported by the National Natural Science Foundation of China(No.29872010)the Natural Science Foundation of Zhejiang Province(No.298067)
文摘The ? ?vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.
基金Supported by the National Natural Science Foundation of China(No.2 0 372 0 2 4 2 0 172 0 18) +2 种基金the Excellent ScientistFoundation of Anhui ProvinceChina(No.2 0 0 10 4 0 ) the Natural Science Foundation of the Educational Departm entof AnhuiProvince
文摘Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides with metallic zinc powder in aqueous media has been developed, which generates E-alkenes with excellent yields. The reactivity of vic-dibromides decreases in the order of 1,2-dibromo-1,2-diphenylethane>1,2-dibromo-1-phenylethane>1,2-dibromo-1,2-dialkylethane.
文摘The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.
文摘Hydrozirconation of 1-alkylnylphosphonates gives the organozirconium(Ⅳ) complexes 2 in syn-addition way. Complexs 2 was trapped with NCS, NBS or I2 to afford stereodifined α-halo-1-alkenylphosphonates in moderate to high yields.
文摘The palladium catalyzed hydrostannation of 1-alkenylphosphonates gives the (E)-α-stannyl 1-alkenylphosphonates 2 stereospecifically. Compounds 2 can occur Stille coupling reaction to afford a, b-disubstituted vinylphosphonates with the retention of the configuration.
文摘Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) to afford α,α'-bis(substituted benzylidene) cycloalkanones in good yields.
基金theNationalNaturalScienceFoundationofChina (No .2 9872 0 10 )theNaturalScienceFoundationofZhejiangProvinceChina (No .2 0 0 72 0 33)
文摘bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China The differently substituted aromatic nitro compounds were chemoselectively reduced by Sm/HOAc system in an ionic liquid medium to afford aromatic amines. Under these conditions the other substituents, such as -X, -CHO, -COOH, -CN, -NHTos and -alkyl, remained intact. The notable advantages of this reaction are its mild conditions, simple operation, short reaction time, high yields and easy recycling of ionic liquid.
文摘A general and practical procedure for the syntheses of 3,4 dihydropyrimidine 2(1 H ) thiones by a one pot condensation of aldehyde, β ketoester or β diketone and thiourea using La (OTf) 3 as the catalyst is described. Mild reaction conditions, excellent yields as well as the environmentally friendly character of La(OTf) 3 make it an important alternative to the classic acid catalyzed Biginelli's reaction.
文摘Lanthanide compounds have been attracting much attention in organic synthesis. Chiral Ln substituted BINOL have been widely studied in several asymmetric organic reactions. LnCl 3 and Ln(OTf) 3 have been expected to serve as Lewis acids and have been applied to many important synthetic reactions in a one pot manner. Ln(O i Pr) 3 exhibits some basic characters, which also can be utilized in some special organic transformation. This article deals with some lanthanides(III) complexes promoted organic reactions, which we have recently developed.
文摘A variety of lanthanocene complexes, e.g. chlorides, hydrocarbyls, amides, hydrides and divalent derivatives, were synthesized by using a series of designed cyclopentadienyl, indenyl and fluorenyl ligands with ring bridges or dornor functionalized sidearms. X Ray crystallographic analyses reveal the formation of intramolecular coordination bonds between central metals and heteroatoms (O, N) in sidearms or bridging chains. Some applications of these complexes are also discussed in this account.
