Reaction mechanisms: pericyclic reactions

Tantillo, Dean J.; Lee, Jeehiun K.

doi:10.1039/c1oc90004h

Cited by 7 publications

(2 citation statements)

References 57 publications

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“…Since the 1,3-dipolar cycloadditions are synthetically challenging, , provide the possibility of catalytic improvements, − and lead to desirable products, − investigations are in the hundreds and beyond what can be cited here. We focus in this work on the quantum chemical investigations, as they can provide a direct insight into the mechanism of the 1,3-dipolar cycloadditions. − Whenever the computational description of pericyclic reactions has to be considered, then the work of Houk and his co-workers deserves special mentioning, and this also holds for the 1,3-dipolar cycloadditions. − So far, the mechanism of these cycloadditions has been investigated from a general point of view, ,, where specific features such as the energetics, ,− kinetic aspects, regio- and stereoselectivity, ,,,, concertedness, ,, or nonconcertedness in the presence of radical-stabilizing groups ,, are reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

“…28−40 Whenever the computational description of pericyclic reactions has to be considered, then the work of Houk and his co-workers deserves special mentioning, and this also holds for the 1,3-dipolar cycloadditions. 41−59 So far, the mechanism of these cycloadditions has been investigated from a general point of view, 52,60,61 where specific features such as the energetics, 48,53−55 kinetic aspects, 43 regio-and stereoselectivity, 28,30,36,47,62 concertedness, 40,45,46 or nonconcertedness in the presence of radical-stabilizing groups 44,50,63 are reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Reaction Valley Investigation of the Cycloaddition of 1,3-Dipoles with the Dipolarophiles Ethene and Acetylene: Solution of a Mechanistic Puzzle

Sexton¹,

Freindorf²,

Kraka

2016

J. Phys. Chem. A

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The reaction mechanism of the cycloaddition of ten 1,3-dipoles with the two dipolarphiles ethene and acetylene is investigated and compared using the unified reaction valley approach (URVA) in a new form, which is based on a dual level strategy, an accurate description of the reaction valley far out into the van der Waals region, and a comparative analysis of the electronic properties of the reaction complex. A detailed one-to-one compar- ison of 20 different 1,3-dipolar cycloadditions is carried out and so far unknown mechanistic features are revealed. There are significant differences in the reaction mechanisms for the two dipolarophiles that result from the van der Waals complex formation in the entrance channel of the cycloadditions. Hydrogen bonding between the 1,3-dipole and acetylene is generally stronger, which leads to higher reaction barriers in the acetylene case. Elementary differences are found with regard to charge transfer, charge polarization, rehybridization, and bond formation of the two dipolarophiles, which explain their different reaction energies. It is shown that similarities in the reaction barriers as determined by CCSD(T)-F12/aug-cc- pVTZ calculations are accidental because of a fortuitous cancellation of different electronic effects. In general, a caveat has to be made with regard to oversimplified descriptions of the reaction mechanism based on orbital theory or energy decomposition schemes.

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