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タイトル: A new intermediate in the Prins reaction.
著者: Yamabe, Shinichi
Fukuda, Takeshi
Yamazaki, Shoko
著者名の別形: 山邊, 信一
キーワード: DFT calculations
hemiacetal intermediate
hydrogen bond
Prins reaction
transition state
発行日: 5-Mar-2013
出版者: Beilstein-Institut
誌名: Beilstein journal of organic chemistry
巻: 9
開始ページ: 476
終了ページ: 485
抄録: Two Prins reactions were investigated by the use of DFT calculations. A model composed of R-CH=CH2 + H3O(+)(H2O)13 + (H2C=O)2, R = Me and Ph, was adopted to trace reaction paths. For both alkenes, the concerted path forming 1,3-diols was obtained as the rate determining step (TS1). TS stands for a transition state. From the 1,3-diol, a bimolecular elimination (TS2) leads to the allylic alcohol as the first channel. In the second channel, the 1,3-diol was converted via TS3 into an unprecedented hemiacetal intermediate, HO-CH2-O-CH(R)-CH2-CH2-OH. This intermediate undergoes ring closure (TS4), affording the 1,3-dioxane product. The intermediate is of almost the same stability as the product, and two species were suggested to be in a state of equilibrium. While the geometry of TS1 appears to be forwarded to that of a carbocation intermediate, the cation disappeared through the enlargement of the water cluster. Dynamical calculations of a classical trajectory using the atom-centered density matrix propagation molecular dynamics model on the four TSs were carried out, and results of IRC calculations were confirmed by them.
著作権等: © 2013 Yamabe et al; licensee Beilstein-Institut.
This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc)
URI: http://hdl.handle.net/2433/173363
DOI(出版社版): 10.3762/bjoc.9.51
PubMed ID: 23532354
出現コレクション:学術雑誌掲載論文等

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