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note
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It is immediately evident that TS-23n forms a bond from C3 to the proximal allyl terminus. Although it appears feasible that TS-23x might involve rotation of the distal allyl carbon past C4 and into bonding distance with C3, IRC calculations show that this is not the case: the bond is formed to the proximal carbon in TS-23x as well as TS-23n.
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20
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20544463652
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note
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21 is the same for all intermediates 2, and therefore may be ignored in the computation of label distribution in product 3.
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21
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20544434371
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A transition state for a concerted [3s,3s] reaction, as well as one for a concerted [1i,3s] process, can be located with RB3LYP/6-31G(d) (Supporting Information), but these saddle points are only artifacts of the restricted formalism, and they disappear at the UB3 LYP level.
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22
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20544456350
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note
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A CASPT2 single-point energy calculation was performed on each of the UB3 LYP constrained-optimized structures used to construct the UB3 LYP surface.
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23
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0037055058
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A PES involving a post-TS bifurcation between a Cope pathway and formation of an allylic-stabilized diradical intermediate has been discussed in the case of an acyclic allenic triene: S. L. Debbert, B. K. Carpenter, D. A. Hrovat, W. T. Borden, J. Am. Chem. Soc. 2002, 124, 7896.
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