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0000324982
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Endo addition involves the tendency for dienophile substituents to be so oriented in the favored transition state that they lie directly above the residual unsaturation of the diene see
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Endo addition involves the tendency for dienophile substituents to be so oriented in the favored transition state that they lie directly above the residual unsaturation of the diene (see: Martin, J. G.; Hill, R. K. Chem. Rev. 1961, 61, 537-562).
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Martin, J.G.1
Hill, R.K.2
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16
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70349088859
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note
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Syn being defined as an attack from the same side of the diene system as the previously incorporated dienophile ring is located. Conversely, anti means from the other side.
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17
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33846216479
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For the synthesis of the starting compounds 1, see
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For the synthesis of the starting compounds 1, see: Požgan, F.; Kranjc, K.; Kepe, V.; Polanc, S.; Kočevar, M. ARKIVOC 2007, 8, 97-111.
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Požgan, F.1
Kranjc, K.2
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Polanc, S.4
Kočevar, M.5
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(a) Microwaves in Organic Synthesis; Loupy, A., Ed.; Wiley-VCH: Weinheim, Germany, 2002.
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28
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70349119749
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note
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The C-form (cisoid) of the intermediate 4C is defined as the one where the ring of dienophile is on the same side of the diene system as the cyclooctene ring is bent to. In the T-form (transoid) one ring is on the opposite side. See Figure 1.
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29
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0038626673
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et al. Revision B.03; Gaussian, Inc., Wallingford, CT
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Gaussian 03
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Frisch, M.J.1
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30
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70349142491
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note
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According to AM1 and PM3 calculations, exo,endo adduct 6Ce is thermodinamcally more stable than exo,exo adduct 5Ce by approximately 5 kcal/mol. Therefore, this process seems to take place under kinetic control yielding the adduct via the endo,anti attack.
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31
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70349135750
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note
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Aromatization takes place via the transfer of hydrogen to the 2e, thus forming succinic anhydride (for a related case forming substituted succinimides from maleimides, as observed previously, see ref 2d).
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32
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70349108219
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note
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Numbering sequences for compounds 5Aa, 5Bb, and 6Ca are the following: (Chemical Equation Presented)
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33
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0033474114
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(a) Obata, T.; Shimo, T.; Yoshimoto, S.; Somekawa, K.; Kawaminami, M. Chem. Lett. 1999, 181-182.
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35
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70349134168
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note
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For the other general experimental details and characterization data for all synthesized compounds, see the Supporting Information.
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