The Cope Rearrangement of 1,5-Dimethylsemibullvalene-2(4)-d1: Experimental Evidence for Heavy-Atom Tunneling

Schleif, T.; Mieres-Perez, J.; Henkel, S.; Ertelt, M.; Borden, W. T.; Sander, W., Angew. Chem. Int. Ed. 2017, 56, 10746-10749
Contributed by Steven Bacharach
Reposted from Computational Organic Chemistry with permission

Another prediction made by quantum chemistry has now been confirmed. In 2010, Zhang, Hrovat, and Borden predicted that the degenerate rearrangement of semibullvalene 1 occurs with heavy atom tunneling.¹ For example, the computed rate of the rearrangement including tunneling correction is 1.43 x 10^-3 s^-1 at 40 K, and this rate does not change with decreasing temperature. The predicted half-life of 485 s is 10¹⁰ shorter than that predicted by transition state theory.

Now a group led by Sander has examined the rearrangement of deuterated 2.² The room temperature equilibrium mixture of d⁴–2 and d²–2 was deposited at 3 K. IR observation showed a decrease in signal intensities associated with d⁴–2 and concomitant growth of signals associated with d²–2. The barrier for this interconversion is about 5 kcal mol^-1, too large to be crossed at this temperature. Instead, the interconversion is happening by tunneling through the barrier (with a rate about 10^-4 s^-1), forming the more stable isomer d²–2 preferentially. This is exactly as predicted by theory!

References

1. Zhang, X.; Hrovat, D. A.; Borden, W. T., "Calculations Predict That Carbon Tunneling Allows the Degenerate Cope Rearrangement of Semibullvalene to Occur Rapidly at Cryogenic Temperatures." Org. Letters 2010, 12, 2798-2801, DOI: 10.1021/ol100879t.

2. Schleif, T.; Mieres-Perez, J.; Henkel, S.; Ertelt, M.; Borden, W. T.; Sander, W., "The Cope Rearrangement of 1,5-Dimethylsemibullvalene-2(4)-d1: Experimental Evidence for Heavy-Atom Tunneling." Angew. Chem. Int. Ed. 2017, 56, 10746-10749, DOI: 10.1002/anie.201704787.

InChIs

1: InChI=1S/C8H8/c1-3-6-7-4-2-5(1)8(6)7/h1-8H
InChIKey=VEAPRCKNPMGWCP-UHFFFAOYSA-N

d⁴–2: InChI=1S/C10H12/c1-9-5-3-7-8(4-6-9)10(7,9)2/h3-8H,1-2H3/i5D
InChIKey=WUJOLJNLXLACNA-UICOGKGYSA-N

d²–2: InChI=1S/C10H12/c1-9-5-3-7-8(4-6-9)10(7,9)2/h3-8H,1-2H3/i7D
InChIKey=WUJOLJNLXLACNA-WHRKIXHSSA-N

'
This work is licensed under a Creative Commons Attribution-NoDerivs 3.0 Unported License.