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Vol. 26 No. 4 (2014): Vol 26 Issue 4

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Theoretical Study on Synthesis of Sylvestrene by Cyclodimerization of Isoprene: Asynchronous Concerted Mechanism of Diels-Alder Reaction

https://doi.org/10.14233/ajchem.2014.15814
Chuan-Ming Wang
Key Lab of Tobacco Chemistry of Yunnan, Yunnan Academy of Tobacco Science, Kunming 650000, P.R. China ;University Key Laboratory of Crop High Quality, Effective Cultivation and Safety Control in Yunnan Province, Honghe University, Mengzi 661100, P.R. China Modern Biological Research Center, Yunnan University, Kunming 650091, P.R. China ;These authors contributed equally to these work.
Yi-Lei Chen
Modern Biological Research Center, Yunnan University, Kunming 650091, P.R. China ;These authors contributed equally to these work.
Zhi-Hua Liu
Key Lab of Tobacco Chemistry of Yunnan, Yunnan Academy of Tobacco Science, Kunming 650000, P.R. China
Yong-Kuan Chen
Key Lab of Tobacco Chemistry of Yunnan, Yunnan Academy of Tobacco Science, Kunming 650000, P.R. China
Jing-Mei Han
Key Lab of Tobacco Chemistry of Yunnan, Yunnan Academy of Tobacco Science, Kunming 650000, P.R. China
Ming-Ming Miao
Key Lab of Tobacco Chemistry of Yunnan, Yunnan Academy of Tobacco Science, Kunming 650000, P.R. China ;University Key Laboratory of Crop High Quality, Effective Cultivation and Safety Control in Yunnan Province, Honghe University, Mengzi 661100, P.R. China Modern Biological Research Center, Yunnan University, Kunming 650091, P.R. China ;These authors contributed equally to these work.
Huai Cao
Modern Biological Research Center, Yunnan University, Kunming 650091, P.R. China

Corresponding Author(s) : Huai Cao

caohuai@ynu.edu.cn

Asian Journal of Chemistry, Vol. 26 No. 4 (2014): Vol 26 Issue 4

Abstract

Computations on Diels-Alder cycloadditions of sylvestrene from isoprene monomers reveal asynchronous concerted transition structures. The hardness profiles along the intrinsic reaction coordinate present a minimum shift with respect to the transition states. The densities of HOMO and LUMO can explain why the first new bond is formed at the end of double bonds of two isoprenes. All adducts are stereoisomers with similar energies. The asynchronous degree of the endo addition reaction involved in cis-isoprene as dienophile is greater and its potential energy barrier, 10 kJ/mol, is lower than that of any other reaction pathways.

Keywords

Diels-alder reaction Isoprene Asynchronous concerted reaction Hardness Sylvestrene
Wang, C.-M., Chen, Y.-L., Liu, Z.-H., Chen, Y.-K., Han, J.-M., Miao, M.-M., & Cao, H. (2014). Theoretical Study on Synthesis of Sylvestrene by Cyclodimerization of Isoprene: Asynchronous Concerted Mechanism of Diels-Alder Reaction. Asian Journal of Chemistry, 26(4), 1019–1026. https://doi.org/10.14233/ajchem.2014.15814
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