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37549061729
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While probably due to the shallow potential energy surface, it was difficult to find the transition structure for the homolytic cleavage of the N-O bond of 1a; we obtained the biradical structure of 1a in UB3LYP/ 6-31 +G(d,p) calculations, which involved homolytic cleavage of the N-O bond. Formation of the biradical intermediate was endothermic, and the energy difference from 1a is 39.6 kcal/mol (UB3LYP/6-311+G(d,p)// UB3LYP/6-31+G(d,p, This result suggests that the activation energy for the putative biradical formation process, the rate-determining step in the singlet biradical pathway, will be highly energetic as compared with the asynchronous concerted process (30.0 kcal/mol, B3LYP/6-311+G(d,p)// B3LYP/6-31+Gd,p, see Figure S4, Supporting Information
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While probably due to the shallow potential energy surface, it was difficult to find the transition structure for the homolytic cleavage of the N-O bond of 1a; we obtained the biradical structure of 1a in UB3LYP/ 6-31 +G(d,p) calculations, which involved homolytic cleavage of the N-O bond. Formation of the biradical intermediate was endothermic, and the energy difference from 1a is 39.6 kcal/mol (UB3LYP/6-311+G(d,p)// UB3LYP/6-31+G(d,p)). This result suggests that the activation energy for the putative biradical formation process, the rate-determining step in the singlet biradical pathway, will be highly energetic as compared with the asynchronous concerted process (30.0 kcal/mol, B3LYP/6-311+G(d,p)// B3LYP/6-31+G(d,p)) (see Figure S4, Supporting Information).
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5 was not able to be prepared.
-
5 was not able to be prepared.
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-
-
-
57
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37549066288
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2 σ*-orbital (see Table S3 and Figure S5 in the Supporting Information).
-
2 σ*-orbital (see Table S3 and Figure S5 in the Supporting Information).
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58
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37549060991
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Acceleration of the retro-Diels-Alder reaction of 4H-1,2- benzoxazine bearing CF3 at C8 (1l) might be related to the fact that the negative charge of N2 in the reactant 1l, 0.043) is the smallest among the isomers (1g and 1j-l, see Table S2, Supporting Information, This small negative charge of N2 of 1l can be interpreted in terms of the inductive effect of CF3 at C8, which polarizes the electron density of the O1-N2 bond toward the O1 atom. Consequently, the electron-deficient N2 promotes redistribution of the electrons of the C3-C4 bond into the N2-C3 bond (Figure 6, The NPA charge also showed the negative charge of C4 was the highest in 1j among the isomers bearing CF3 at C5 (1j, C6 1k
-
5 (1j) showed the smallest reaction rate among the isomers (1g and 1j-l) (Table 5).
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59
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37549061375
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