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In many computational studies, mechanisms appear to have so-called ambimodal transition states, i.e. a transition state which can lead to multiple products, in conflict to the common undergraduate idea of a reaction pathway.

To give an example, Houk, in Mechanisms and Origins of Periselectivity of the Ambimodal [6 + 4] Cycloadditions of Tropone to Dimethylfulvene,[1] presents the following scheme:

Houk TS for a 6+4 cycloaddition

Reaction pathway for [6 + 4] cycloadditions of Tropone to Dimethylfulvene. Taken from ref [1]

In the scheme, TS-1 may either give 7 (the 'expected' product) or go directly to 6, completely skipping TS-Cope-1 (which would allow 7 and 6 to interconvert) — Houk describes this as an ambimodal transition state, that is one transition state that can lead to two possible products.


Although what he says makes sense, it seems to me that, given 6 is the lower energy product out of the two, it would be favoured thermodynamically anyway.

Upon further reading, I discovered the concept of valley ridge inflection, which appears to describe the phenomenon observed above, in which we completely 'miss' the intermediary transition state:

Valley Ridge inflectio

Why do these ambimodal transition states occur, and how does the situation differ from normal transition state theory?


Notes & References

[1]:Houk, K.N., J. Am. Chem. Soc. 2017, 139, 8251. DOI: 10.1021/jacs.7b02966

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    $\begingroup$ According to Houk (who cites Pierluigi Caramella here) it is one transition state that leads to two products. If you look at the second picture of yours you go through a saddle point and after that you end up on top of another saddle point where you got two direktions to go down. Technically this was one transition state. Do you know this talk: youtu.be/plYVZWBPCws ? It explains a lot of this in detail. The ambimodal cycloadditions start at 1:03, but the part about dynamics before is very helpful $\endgroup$ – DSVA Jul 21 '17 at 22:05
  • $\begingroup$ I haven't seen that talk, some bedtime viewing perhaps! $\endgroup$ – NotEvans. Jul 21 '17 at 22:06

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