The conversion process from bicyclo[4.1.0]heptatriene （BCT） to 1,2,4,6-cycloheptatetraene （CHTE） within a molecular container was studied with AM1 method, and single point energies for all stationary points were e...The conversion process from bicyclo[4.1.0]heptatriene （BCT） to 1,2,4,6-cycloheptatetraene （CHTE） within a molecular container was studied with AM1 method, and single point energies for all stationary points were evaluated by B3LYP and HF methods. The conversion potential barrier for the encapsulation complex became smooth when compared with that for the rearrangement in free state. The influences of the inner phase of the molecular container on the conversion process were discussed.展开更多
The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF（CASSCF） level with a 6-31G^＊ basis set. A muhireference MP2 algorithm that has been implemented in the Gaussian progr...The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF（CASSCF） level with a 6-31G^＊ basis set. A muhireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [ 4.1.0 ] heptane, the reaction is via two bonds＇ breakage to give rise to 1,6-heptdiene. One internal conversion （IC） and two intersystem crossing points（ISC） were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground state.展开更多
Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]he...Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.展开更多
基金This work was supported by the Special Research Fund for the Doctoral Program of Higher Education(20040010008)the Scientific Research Fund of Beijing University of Chemical Technology(QN0411).
文摘The conversion process from bicyclo[4.1.0]heptatriene （BCT） to 1,2,4,6-cycloheptatetraene （CHTE） within a molecular container was studied with AM1 method, and single point energies for all stationary points were evaluated by B3LYP and HF methods. The conversion potential barrier for the encapsulation complex became smooth when compared with that for the rearrangement in free state. The influences of the inner phase of the molecular container on the conversion process were discussed.
基金Supported by the Yunnan Provincial Science and Technology Department(No. 2003A0003M)
文摘The photochemical reaction of bicyclo[4.1.0]heptane was studied at the complete active space SCF（CASSCF） level with a 6-31G^＊ basis set. A muhireference MP2 algorithm that has been implemented in the Gaussian program was used to correct the energetics for the dynamic correlation. Starting from the Franck-Condon excitation of bicyclo [ 4.1.0 ] heptane, the reaction is via two bonds＇ breakage to give rise to 1,6-heptdiene. One internal conversion （IC） and two intersystem crossing points（ISC） were located and are discussed separately. The reaction proceeds to its own characteristic product on the ground state.
文摘Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.
