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. 2009;48(48):9156-9.
doi: 10.1002/anie.200903293.

Recrossing and dynamic matching effects on selectivity in a Diels-Alder reaction

Zhihong Wang  1 , Jennifer S Hirschi, Daniel A Singleton
Affiliations

Recrossing and dynamic matching effects on selectivity in a Diels-Alder reaction

Zhihong Wang et al. Angew Chem Int Ed Engl. 2009.

Abstract

The products from the hetero-Diels-Alder reaction of acrolein with methyl vinyl ketone arise from a single transition state and trajectory studies accurately predict the selectivity. In an extension of the dynamic matching idea of Carpenter, the product formed is determined by the direction of motion passing through the transition state. Recrossing of the cycloaddition transition state occurs extensively and decreases formation of the minor product.

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Figures

Figure 1
Figure 1
TSs of relevance to the reaction of 1 with 2. Four additional high-energy structures are shown in the Supporting Information. Distances shown refer to the MP2/6-311+G**/PCM TSs. Free energies are CCSD(T)/6-31+G**/PCM//MP2/6-311+G**/PCM + a harmonic free-energy estimate for 298 K in kcal/mol. No TS corresponding to 6, defined as an endo s-cis TS leading by MEP to 4, could be located in high-level calculations. TS 9 is for the [3,3]-sigmatropic rearrangement interconverting 4 and 3.
Figure 2
Figure 2
Qualitative potential energy surface in the reaction of 1 with 2. The products 3 and 4 are both downhill from the rate-limiting TS. Trajectories can lead to either product, but the MEP only leads to 3.
Figure 3
Figure 3
Heavy-atom motion associated with the 98-cm−1 mode of 5. Motion in the negative direction moves the structure toward 3 while a positive motion approaches 4.
Figure 4
Figure 4
Outcome of trajectories versus the angle (see text) at which they leave the transition state. On this qualitative potential energy surface, the horizontal axis corresponds to motion along the 98-cm−1 vibrational mode and the orthogonal axis is motion along the transition vector. The arrows labeled a, b, c, and d refer to trajectories within a range of angles: a: <−26°; b: between −26° and 0°; c: between 0° and 26°; d: >26°.
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References

    1. Carpenter BK. Angew Chem. 1998;110:3532–3543.
    2. Angew Chem Int Ed. 1998;37:3340–3350. - PubMed
    3. Carpenter BK. J Phys Org Chem. 2003;16:858–868.
    1. Carpenter BK. J Am Chem Soc. 1985;107:5730–5732.
    2. Carpenter BK. J Am Chem Soc. 1995;117:6336–6344.
    3. Carpenter BK. J Am Chem Soc. 1996;118:10329–10330.
    4. Reyes MB, Carpenter BK. J Am Chem Soc. 2000;122:10163–10176.
    5. Reyes MB, Lobkovsky EB, Carpenter BK. J Am Chem Soc. 2002;124:641–651. - PubMed
    6. Nummela JA, Carpenter BK. J Am Chem Soc. 2002;124:8512–8513. - PubMed
    7. Litovitz AE, Keresztes I, Carpenter BK. J Am Chem Soc. 2008;130:12085–12094. - PMC - PubMed
    1. Doubleday C, Jr, Bolton K, Hase WL. J Am Chem Soc. 1997;119:5251–5252.
    2. Doubleday C, Nendel M, Houk KN, Thweatt D, Page M. J Am Chem Soc. 1999;121:4720–4721.
    3. Doubleday C, Suhrada CP, Houk KN. J Am Chem Soc. 2006;128:90–94. - PubMed
    1. Kless A, Nendel M, Wilsey S, Houk KN. J Am Chem Soc. 1999;121:4524–4525.
    2. Debbert SL, Carpenter BK, Hrovat DA, Borden WT. J Am Chem Soc. 2002;124:7896–7897. - PubMed
    1. Metiu H, Ross J, Silbey R, George TF. J Chem Phys. 1974;61:3200–3209.
    2. Valtazanos P, Ruedenberg K. Theor Chim Acta. 1986;69:281–307.
    3. Windus TL, Gordon MS, Burggraf LW, Davis LP. J Am Chem Soc. 1991;113:4356–4357.
    4. Tachibana A, Okazaki I, Koizumi M, Hori K, Yamabe T. J Am Chem Soc. 1985;107:1190–1196.
    5. Zhou C, Birney DM. Org Lett. 2002;4:3279–3282. - PubMed
    6. Wei H, Hrovat DA, Borden WT. J Am Chem Soc. 2006;128:16676–16683. - PubMed
    7. Shaik S, Danovich D, Sastry GN, Ayala PY, Schlegel HB. J Am Chem Soc. 1997;119:9237–9245.

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