Archive for January, 2014

Another example of tunneling control

The notion of tunneling control has been a topic of interest within this blog a number of times. As developed by Schreiner and Allen,1,2 tunneling control is a third means for predicting (or directing) the outcome of a reaction, alongside the more traditionally recognized kinetic and thermodynamic control. Tunneling control occurs when tunneling through a higher barrier is preferred over tunneling through a lower barrier.

Kozuch and Borden propose another example of tunneling control, this time in the rearrangement of the noradamantyl carbene 1.3 This carbene can undergo a 1,2-carbon shift, driven by strain relief to form the alkene 2. The alternative as a 1,2-hydrogen shift that produces the alkene 3.

These two reaction pathways were explored using B3LYP/6-31G(d,p) computations coupled with canonical variational theory and small curvature tunneling corrections. Structures of the reactant 1 and the two transition states leading to the two products 2 and 3 are shown in Figure 1. The activation barrier at 300 K is 5.4 kcal mol-1 leading to 2 and 8.6 kcal mol-1 leading to 3. Tunneling is expected to be much more important for the hydrogen shift than for the carbon shift, but even including tunneling, the rate to form 2 is much faster than the rate to form 3 at 300 K.


TS 1→2


TS 1→3


Figure 1. B3LYP/6 optimized structures of 1-3 and the transition states leading to 2 and 3.

The situation is reversed however at cryogenic temperatures (< 20 K). Tunneling is now the only route for the reactions to occur, and the rate for formation of 3 is dramatically greater than the rate of formation of 2, which is inhibited by the movement of the much heavier carbon atom. Perdeuteration of the methyl group of 1, which drastically slows the rate of tunneling in the path to 3, nonetheless still favors this pathway (forming d33) over formation of d32. Thus, at low temperatures the formation of 3 is the preferred product, a manifestation of tunneling control.

Kozuch and Borden end their paper with a hope that an experimentalist will examine this interesting case. I concur!


(1) Schreiner, P. R.; Reisenauer, H. P.; Ley, D.; Gerbig, D.; Wu, C.-H.; Allen, W. D. "Methylhydroxycarbene: Tunneling Control of a Chemical Reaction," Science 2011, 332, 1300-1303, DOI: 10.1126/science.1203761.

(2) Ley, D.; Gerbig, D.; Schreiner, P. R. "Tunnelling control of chemical reactions – the organic chemist’s perspective," Org. Biomol. Chem. 2012, 10, 3781-3790, DOI: 10.1039/C2OB07170C.

(3) Kozuch, S.; Zhang, X.; Hrovat, D. A.; Borden, W. T. "Calculations on Tunneling in the Reactions of Noradamantyl Carbenes," J. Am. Chem. Soc. 2013, 135, 17274-17277, DOI: 10.1021/ja409176u.


1: InChI=1S/C11H16/c1-2-11-6-8-3-9(7-11)5-10(11)4-8/h8-10H,3-7H2,1H3

2: InChI=1S/C11H16/c1-7-10-3-8-2-9(5-10)6-11(7)4-8/h8-10H,2-6H2,1H3

3: InChI=1S/C11H16/c1-2-11-6-8-3-9(7-11)5-10(11)4-8/h2,8-10H,1,3-7H2

Borden &Tunneling Steven Bachrach 27 Jan 2014 No Comments

Is the cyclopropenyl anion antiaromatic?

The concept of antiaromaticity is an outgrowth of the well-entrenched notion or aromaticity. While 4n+2 π-electron systems are aromatic, 4n π-electron systems should be antiaromatic. That should mean that antiaromatic systems are unstable. The cyclopropenyl anion 1a has 4 π-electrons and should be antiaromatic. Kass has provided computational results that strongly indicate it is not antiaromatic!1

Let’s first look at the 3-cyclopropenyl cation 1c. Kass has computed (at both G3 and W1) the hydride affinity of 1c-4c. The hydride affinities of the latter three compounds plotted against the C=C-C+ angle is linear. The hydride affinity of 1c however falls way below the line, indicative of 1c being very stable – it is aromatic having just 2 π-electrons.

A similar plot of the deprotonation enthalpies leading to 1a-4d vs. C=C-C angle is linear including all four compounds. If 1a where antiaromatic, one would anticipate that the deprotonation energy to form 1a would be much greater than expected simply from the effect of the smaller angle. Kass suggests that this indicates that 1a is not antiaromatic, but just a regular run-of-the-mill (very) reactive anion.

A hint at what’s going on is provided by the geometry of the lowest energy structure of 1a, shown in Figure 1. The molecule is non-planar, having Cs symmetry. A truly antiaromatic structure should be planar, really of D3h symmetry. The distortion from this symmetry reduces the antiaromatic character, in the same way that cyclobutadiene is not a perfect square and that cyclooctatraene is tub-shaped and not planar. So perhaps it is more fair to say that 1a has a distorted structure to avoid antiaromaticity, and that the idealized D3h structure, does not exist because of its antiaromatic character.

Figure 1. G3 optimized geometry of 1a.


(1) Kass, S. R. "Cyclopropenyl Anion: An Energetically Nonaromatic Ion," J. Org. Chem. 2013, 78, 7370-7372, DOI: 10.1021/jo401350m.


1a: InChI=1S/C3H3/c1-2-3-1/h1-3H/q-1

1c: InChI=1S/C3H3/c1-2-3-1/h1-3H/q+1

Aromaticity &Kass Steven Bachrach 20 Jan 2014 2 Comments

Chiral aromatics

Naphthalene, phenanthrene and pyrene are all planar aromatic compounds. How can substituted version be chiral, with the chirality present in the aromatic portion of the molecule? The answer is provided by Yamaguchi and Kwon.1 They prepared peri-substituted analogues with the bulky adamantly group as the substituents. This bulky requires one adamantyl group to be position above the aromatic plane and the other below the plane, as in 1 and 2.



These molecules and two other examples were prepared in their optically pure form. B3LYP/6-31G(d) computations were performed on both of these structures (shown in Figure 1), but computations are a minor component of the work. These structures do show the out-of-plane distortions at C1 and C8, also apparent in the crystal structures. Computations of naphthalene and 1,8-dimethylnaphthalene show a planar naphthalene backbone, but -propyl substitution does force the substituents out of plane.



Figure 1. B3LYP/6-31G(d) optimized structures of 1 and 2.

These types of systems continue to subject the notion of “aromaticity” to serious scrutiny.


(1) Yamamoto, K.; Oyamada, N.; Xia, S.; Kobayashi, Y.; Yamaguchi, M.; Maeda, H.; Nishihara, H.; Uchimaru, T.; Kwon, E. "Equatorenes: Synthesis and Properties of Chiral Naphthalene, Phenanthrene, Chrysene, and Pyrene Possessing Bis(1-adamantyl) Groups at the Peri-position," J. Am. Chem. Soc. 2013, 135, 16526-16532, DOI: 10.1021/ja407800e.


1: InChI=1S/C30H36/c1-3-25-4-2-6-27(30-16-22-10-23(17-30)12-24(11-22)18-30)28(25)26(5-1)29-13-19-7-20(14-29)9-21(8-19)15-29/h1-6,19-24H,7-18H2

2: InChI=1S/C36H38/c1-2-27-4-5-28-6-7-30(35-15-21-8-22(16-35)10-23(9-21)17-35)34-31(14-29(3-1)32(27)33(28)34)36-18-24-11-25(19-36)13-26(12-24)20-36/h1-7,14,21-26H,8-13,15-20H2

Aromaticity Steven Bachrach 06 Jan 2014 5 Comments