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Single point calculations using Spartan at the RB3LYP level show an energy difference of 17.7 kcal/mol between the more stable endo product 3g and the less stable exo product 2g.
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Single point calculations using Spartan at the RB3LYP level show an energy difference of 17.7 kcal/mol between the more stable endo product 3g and the less stable exo product 2g.
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See Supporting Information for details
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See Supporting Information for details.
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N′ reaction of allylic iodides, see: McDowell, C. A.; Lossing, F. P.; Henderson, I. H. S.; Farmer, J. B. Can. J. Chem. 1956, 34, 345.
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N′ reaction of allylic iodides, see: McDowell, C. A.; Lossing, F. P.; Henderson, I. H. S.; Farmer, J. B. Can. J. Chem. 1956, 34, 345.
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43
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33947448784
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Although the major route of isomerization is likely via Su2' attack of iodide, there is a possibility that trace !2, either generated in situ or as an impurity in the commercial MgI2, could lead to allylic iodide isomerization. For instance, see: (a) Sibbett, D. J, Noyes, R. M. J. Am. Chem. Soc. 1953, 75, 761
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2, could lead to allylic iodide isomerization. For instance, see: (a) Sibbett, D. J.; Noyes, R. M. J. Am. Chem. Soc. 1953, 75, 761.
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33751554315
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Although an SN2′ ring-closing pathway (5-endo-trig) is unfavored by Balwin's rules, similar 5-endo-trig ring-closing reactions have been reported for the synthesis of pyrrolidines. See, for example: (a) Padwa, A, Norman, B. H. J. Org. Chem. 1990, 55, 4801
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1 H NMR analysis showed only 2k along with unreacted starting material. Extensive formation of the endo isomer (3k) along with significant amounts of decomposition were observed after prolonged heating.
-
1 H NMR analysis showed only 2k along with unreacted starting material. Extensive formation of the endo isomer (3k) along with significant amounts of decomposition were observed after prolonged heating.
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54
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33846004930
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2O are used to reverse this selectivity. See, for example: (a) Ferrer. M.; Sànchez-Baeza, F.; Messeguer, A.; Diez, A.; Rubiralta, M. J. Chem. Soc. Chem. Commun. 1995, 293.
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