The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed ...The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.展开更多
The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr =...Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) ?, α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) ?3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.展开更多
The adsorption of CH3CN and CH3NC on the Pt(111)surface at the 1/4 monolayer(ML)coverage has been carried out at the level of density functional theory for understanding hydrogenation processes of nitriles.The most fa...The adsorption of CH3CN and CH3NC on the Pt(111)surface at the 1/4 monolayer(ML)coverage has been carried out at the level of density functional theory for understanding hydrogenation processes of nitriles.The most favored adsorption structure for CH3CN is the C-N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms.For CH3NC,the most stable configuration is the CH3NC locates at the face center cubic(fcc)site with the C-atom bonded to three Pt atoms.In addition,the HCN and HNC adsorption has been computed,and the adsorption pattern is nearly similar to the CH3CN and CH3NC,respectively.The adsorbed molecules rehybridize on the surface,becoming non-linear with a bent C-C-N or C-N-C angle.Furthermore,the binding mechanism of these molecules on the Pt(111)surface is also analyzed.展开更多
A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly ...A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.展开更多
A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. T...A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. The reaction employing easily available starting materials features simple operation and high efficiency. The mechanistic study showed that the reaction might undergo 1) Pd-catalyzed [3+2] cyclization of o-bromobenzaldehyde with isocyanide and the re-insertion of another molecule of isocyanide,2) addition of carboxylic acid to in situ formed ketenimine followed by a rearrangement relay to give 3,3-diacyl-substituted isoindolinone derivative. Further transformations of the obtained products through decarbonylation could also be realized.展开更多
A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into ...A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the sevenmembered azepinone ring.展开更多
基金supported by the National Natural Science Foundation of China (No.11174215)
文摘The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.
文摘The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
基金This work was supported by NSF of Fujian Province (E0420002 and E0310029)
文摘Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) ?, α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) ?3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.
基金Natural Science Foundation of Shanxi Province(No. 2009011014)
文摘The adsorption of CH3CN and CH3NC on the Pt(111)surface at the 1/4 monolayer(ML)coverage has been carried out at the level of density functional theory for understanding hydrogenation processes of nitriles.The most favored adsorption structure for CH3CN is the C-N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms.For CH3NC,the most stable configuration is the CH3NC locates at the face center cubic(fcc)site with the C-atom bonded to three Pt atoms.In addition,the HCN and HNC adsorption has been computed,and the adsorption pattern is nearly similar to the CH3CN and CH3NC,respectively.The adsorbed molecules rehybridize on the surface,becoming non-linear with a bent C-C-N or C-N-C angle.Furthermore,the binding mechanism of these molecules on the Pt(111)surface is also analyzed.
基金the National Natural Science Foundation of China(Nos.22171178, 21871174, 22071143)Innovation Program of Shanghai Municipal Education Commission (No.2019–01–07–00–09-E00008) for financial support。
文摘A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.
基金the National Natural Science Foundation of China(Nos.21772138 and 21672157)the Natural Science Foundation of Jiangsu Province(BK20221356)PAPD。
文摘A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. The reaction employing easily available starting materials features simple operation and high efficiency. The mechanistic study showed that the reaction might undergo 1) Pd-catalyzed [3+2] cyclization of o-bromobenzaldehyde with isocyanide and the re-insertion of another molecule of isocyanide,2) addition of carboxylic acid to in situ formed ketenimine followed by a rearrangement relay to give 3,3-diacyl-substituted isoindolinone derivative. Further transformations of the obtained products through decarbonylation could also be realized.
基金Financial support from the National Natural Science Foundation of China (Nos. 22001151, 22171168, 22101159)Taishan Scholar Program of Shandong Province and Shandong Provincial Natural Science Foundation (Nos. ZR2019QB004, ZR2020QB019) is gratefully acknowledged。
文摘A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the sevenmembered azepinone ring.
