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0043025740
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note
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The terminology syn/anti indicates the spatial arrangement of the alkoxy group at C-5 and the pyrazoline ring at the furanone moiety. It also indicates that the approach of the dipole has taken place either to the face containing the alkoxy group (syn-approach) or to the opposite one (anti-approach). Therefore, the syn/anti ratio will be indicative of the π-facial selectivity of the reaction. The term exo indicates the trans arrangement of the methyl group of the diazoethane with respect to the furanone moiety at the pyrazoline ring. It is characteristic of the exo approach of the dipole to the dipolarophile, using as the reference the carbonyl group at the later.
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15
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0041522945
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note
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As the isolation of 1b in its diastereomerically pure form was very difficult these reactions were performed starting from a 94:6 mixture of 1b and 1a. As a consequence, in all cases we also obtained small amounts (∼6%) of the adduct syn-4a-exo, which could be easily separable from the 4b adducts.
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16
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0042524784
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note
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The data corresponding to this reaction in ref 3 indicate that anti-5b was exclusively formed under the conditions indicated in entry 6. However, taking into account that compound syn-4b-exo resulted from the approach of the diazoethane to the face of the dipolarophile bearing the OEt group at C-5, the absence of a similar adduct (syn-5b) in the reaction of 1b with the less hindered diazomethane was difficult to explain. Therefore, we have repeated the later reaction and thoroughly studied the reaction crude, with the results indicated in entry 6 of Table 2. This mistake was responsible for the wrong conclusions reported in ref 3,
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17
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0042023916
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note
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This contrasts with the previously reported proposal in ref 3, which assumed that the π-facial selectivity was exclusively controlled by the sulfinyl configuration through the steric effects present in the most stable conformation around the C-S bond.
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18
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0043025716
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note
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Taking into account that the carbonated end at the dipole supports a negative charge, initially we thought that the alkoxy oxygen could exhibit a possitive charge as a consequence of the strong anomeric effect present in 5-alkoxy-furan-2-(5H)-ones, but further theoretical calculations revealed that this was not the case.
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19
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0000497411
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Fariña, F.; Martín, M. V.; Sánchez, F. Heterocycles 1986, 24, 2587-2592.
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Rispens, M. T.; Keller, E.; de Lange, B.; Zijlstra, R. W. J.; Feringa, B. L. Tetrahedron: Asymmetry 1994, 5, 607-624 and references therein.
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21
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0041522913
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note
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These data suggest that the results published in ref 16, concerning the π-facial selectivity of the reaction of 5-methoxy-2(5H)-furanone with diazomethane at -10 °C (30:70 syn:anti), could be wrong. On the other hand, the stereoselectivity reported in ref 17 for reactions of 5-(l)-menthyloxy-2(5H)-furanone with diazomethane (40: 60 syn:anti) is not consistent with that of ref 16 from a steric point of view (as the menthyloxy group is bulkier than the methoxy one, a higher proportion of the anti-adduct must be expected in the former case).
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The steric differentiation of the diastereotopic faces at the furanone ring produced by the OMe group at C-5 was able to control the π-facial selectivity of their reactions with cyclopentadiene (Feringa, B. L.; de Jong, J. C. J. Org. Chem. 1988, 53, 1125-1127).
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