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Recently, a rhodium-catalyzed reaction affording 2, H, -azirines as products has been reported
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The 2H-pyrrole 3 a was also obtained as a by-product, but in <6 % yield in all cases, thus indicating that a nitrene intermediate could react with the reactive site, such as an alkene moiety, in this reaction system.
-
The 2, H, -pyrrole, 3 a, was also obtained as a by-product, but in <6 % yield in all cases, thus indicating that a nitrene intermediate could react with the reactive site, such as an alkene moiety, in this reaction system
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52
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85099670744
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3], did not exhibit catalytic activity towards 2H-azirine formation (yields of 2 b were <5 %).
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Other transition metal catalysts, for example [Pd(PPh, ], [RhCl(PPh, ][RuCl, (PPh, ], did not exhibit catalytic activity towards 2, H, -azirine formation (yields of, 2 b, were <5 %)
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Nishimura et al. have suggested the involvement of homolytic N−O bond cleavage in the iridium(I)-catalyzed reaction. The present reaction might also involve a radical pathway in the racemization of the intermediates
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Nishimura et al. have suggested the involvement of homolytic N−O bond cleavage in the iridium(I)-catalyzed reaction. The present reaction might also involve a radical pathway in the racemization of the intermediates. See: T. Nishimura, T. Yoshinaka, Y. Nishiguchi, Y. Maeda, S. Uemura, Org. Lett. 2005, 7, 2425.
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Thermodynamic parameters between the reactant (isoxazolone, 1 p) and the products (azirine, 2 p, and carbon dioxide) at 25 °C (298 K) were estimated with DFT calculations at B3LYP/6-31G(d,p) level (Δ, G, =−14.0 kcal mol, H, =−1.8 kcal mol, S, =41.0 cal mol, ⋅K)
-
−1[1d]).
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These values indicate that the decarboxylation process will stabilize the products in both enthalpy and entropy, despite the formation of highly strained 2, H, -azirines (calculated strain energy=ca. 45–48 kcal mol
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