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L.R. Domingo, M. Arno, P. Merino, and T. Tejero Eur. J. Org. Chem. 2006 3464 3472 There is another report on this reaction (see: Milet, A.; Gimbert, Y.; Greene, A. E. J. Comput. Chem. 2006, 27, 157-162). However, this report, carried out with very simple models far from actual reaction systems, did not consider the presence either Lewis acids or solvent, claiming a concerted mechanism. In our previous study we demonstrated (both theoretically and experimentally) that the reaction in the absence of any Lewis acid is not possible, a stepwise mechanism being much more favourable when a Lewis acid is present and solvent interactions are considered
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98
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78951470705
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It is also possible to consider rotation along the opposite pathway. However, this possibility was discarded because it led to the intermediate orthoester formed through TS3, which is not actually obtained. This route was clearly energetically unfavoured (see below).
-
It is also possible to consider rotation along the opposite pathway. However, this possibility was discarded because it led to the intermediate orthoester formed through TS3, which is not actually obtained. This route was clearly energetically unfavoured (see below).
-
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99
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78951493196
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We have carried out the full theoretical study in the gas-phase, which is necessary for introducing solvation correction. These results as well as additional calculations considering introduction of diffuse functions and solvation effects for pathways corresponding to higher TSs, including the concerted pathway, are available from the authors on request. Diez-Martinez, A. Ph.D. Dissertation, in course.
-
We have carried out the full theoretical study in the gas-phase, which is necessary for introducing solvation correction. These results as well as additional calculations considering introduction of diffuse functions and solvation effects for pathways corresponding to higher TSs, including the concerted pathway, are available from the authors on request. Diez-Martinez, A. Ph.D. Dissertation, in course.
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100
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78951481514
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2 = Me, iPr) are available from the authors on request. Diez-Martinez, A. Ph.D. Dissertation, in course.
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2 = Me, iPr) are available from the authors on request. Diez-Martinez, A. Ph.D. Dissertation, in course.
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