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Gallivan, J. These complexes are illustrated in Figure 2. Career Changes. USA96How to cite this article. Burley, S. Hunter, C. This result suggests that, in biological reactions, the amino acid aromatic side chains in the enzyme active site will not be alkylated by allylic tertiary or secondary intermediates in terpene biosynthesis and that they provide a stabilizing influence on the intermediates. Scenography internship at Proxima du Centaure design studio, in collaboration with Klapisch Claisse scenographers. Intrinsic reaction coordinate calculations IRC were carried out to evaluate whether the transition states connected the reactants to the products.

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    For 2-pentenylium 6the complex formed from the separated carbocation and benzene is exothermic by

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    Their structures are given in Figure 1. The presence of a methyl group attached to C 3as in the case of 3-methylpentenylium 7 and 3-methyl-pentadienylium 9causes an increase of the C 2 -C 3 distance, showing the preference of the charge to be located at C 3.

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    Submitted: February 7, Published online: August 23, In the case of charge transfer, all the three most stable cations among the studied species have the same order of total charges. Peer comments on this answer and responses from the answerer agree.

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    Authors also thank Prof. Hong, Y. Nicholson, H. This result suggests that, in biological reactions, the amino acid aromatic side chains in the enzyme active site will not be alkylated by allylic tertiary or secondary intermediates in terpene biosynthesis and that they provide a stabilizing influence on the intermediates.

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    Zhong, W. In the case of the 2-pentenylium 6one can verify that the C 1 -C 2 and C 2 -C 3 distances are basically the same, showing the same sp 2 character and charge delocalization between these carbon atoms.

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    Burley, S. Pentadienylium 8which has a closer structural similarity to secondary intermediates in terpene biosynthesis, also shows a prominent preferential formation for the non-bonded complex. Kolboe, S.

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