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84962353405
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note
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32 (2.0 kcal/mol) and also quite close to the BLYP value obtained by Schreiner (5.9 kcal/mol). All these values suggest that racemization of 4 is a very fast process (Scheme 3). However, post-HF methods such as BCCD (ref 9d) and CASPT2 and MRCI (ref 34) indicate a higher value of about 10 kcal/mol.
-
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56
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84962374695
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note
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The apparent discrepancy between experimental and theoretical reaction enthalpies has recently been resolved; see ref 34.
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57
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84962374686
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note
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The QCISD/6-311G** barriers to [1,5] H shifts in 1,3-cyclopentadiene and 1,3-pentadiene at 0 K are 29.7 and 40.0 kcal/mol, respectively. See ref 12.
-
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58
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84962374697
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note
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The transition structures 6 and 8 were also computed in ref 19, with geometric results very close to ours.
-
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59
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84962397073
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note
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Hopf/Schreiner found that benzo[c]annulation of cyclohexatriene increased the barrier to aromatization via path b; see ref 9d.
-
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60
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84962437060
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note
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Calculations for this set of points minimizes the effects of σ bonds on NICS.
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84962473325
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84962396394
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1H NMR of the purified product.
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65
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0037041365
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Thermolysis of 1b followed by desilylation gave a 61% yield of 2a and 28% yield of 19 (nondeuterated), this latter confirmed by X-ray analysis. Rodríguez, D.; Navarro-Vázquez, A.; Castedo, L.; Domínguez, D.; Saá, C. Tetrahedron Lett. 2002, 43, 2717-2720.
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84962437080
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note
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5 in benzene, followed by treatment with TBAF).
-
-
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|