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Title
Japanese: 
English:An Absolute Asymmetric Synthesis of the [2 + 2] Cycloadduct via Single Crystal-to- Single Crystal Transformation by Charge-Transfer Excitation of Solid-State Molecular Complexes Composed of Arylolefins and Bis[1,2,5]thiadiazolotetracyanoquino-dimethane 
Author
Japanese: T. Suzuki, 福島 孝典, Y. Yamashita, T. Miyashi.  
English: T. Suzuki, T. Fukushima, Y. Yamashita, T. Miyashi.  
Language English 
Journal/Book name
Japanese: 
English:Journal of the American Chemical Society 
Volume, Number, Page Vol. 116    Issue 7    Page 2793-2803
Published date Apr. 1994 
Publisher
Japanese: 
English: 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
Official URL https://pubs.acs.org/doi/abs/10.1021/ja00086a012
 
DOI https://doi.org/10.1021/ja00086a012
Abstract The title electron acceptor, bis[ 1,2,5] thiadiazolotetracyanoquinodimethane (BTDA, 1), formed weak electrondonor-acceptor (EDA) complexes with arylolefins such as styrene (ST) and divinylbenzenes (DVs). Upon chargetransfer (CT) excitation of these complexes in MeCN, the [2 + 2]-type cycloadducts (2) were formed via a single electron transfer. Similar cycloaddition reactions were efficiently induced when the solid-state molecular complexes of 1 and arylolefins were irradiated. In contrast to the close similarities in solution photochemistry, the solid-state reactivities of three isomeric divinylbenzenes (oDV, mDV, pDV) were quite dissimilar because of the different molecular overlaps of 1 and DVs in the crystal. The apparent reactivity of the oDV- crystal was much higher than that in solution as in the case of the ST-1 crystal, and adduct 2o was formed via the single crystal-to-single crystal transformation. Because of the asymmetric crystal structure in oDV- , the optically pure product with 95% ee was obtained from the achiral components without any external chiral source. On the other hand, the incomplete conversion of the mDV-1 crystal to 2m is due to the crystal-to-amorphous transformation, and the 1:2 adduct 6 was formed on irradiation of the pDV-1 crystal which could not be obtained on excitation of the EDA complex in MeCN.

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