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Fesulphos, Taniaphos, Josiphos, Mandyphos, Solphos, and Phanephos were tested as chiral ligands in this cycloaddition. However, a poor endo/exo selectivity and regioselectivity was observed with all of them (see Scheme below). In addition, all the cycloadditions occurred with low or moderate enantioselectivity, excepting the case of the reaction with Fesulphos (99% ee for exo-4a).
-
Fesulphos, Taniaphos, Josiphos, Mandyphos, Solphos, and Phanephos were tested as chiral ligands in this cycloaddition. However, a poor endo/exo selectivity and regioselectivity was observed with all of them (see Scheme below). In addition, all the cycloadditions occurred with low or moderate enantioselectivity, excepting the case of the reaction with Fesulphos (99% ee for exo-4a).
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f values it was not possible to separate completely exo-4a and the 3-acetyl regioisomer by column chromatography, pure exo-4a was obtained after final recrystallization in isopropanol.
-
f values it was not possible to separate completely exo-4a and the 3-acetyl regioisomer by column chromatography, pure exo-4a was obtained after final recrystallization in isopropanol.
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73449146205
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For a previous example of a switch in the diastereoselectivity of the 1,3-dipolar cycloaddition of azomethine ylides with nitroalkenes varying the electronic properties of the ligands, see ref 6i
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For a previous example of a switch in the diastereoselectivity of the 1,3-dipolar cycloaddition of azomethine ylides with nitroalkenes varying the electronic properties of the ligands, see ref 6i.
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73449144287
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Exo refers to the pyrrolidine with trans stereochemistry at C4-C5. See the Supporting Information for details on the X-ray structure of enantiopure exo-4a. For the configuration of the endo isomer, it has been assumed that the endo/exo cycloaddition occurs with the same π-facial selectivity on the dipole-Cu complex (pyrrolidine adducts with 2S,5S configuration).
-
Exo refers to the pyrrolidine with trans stereochemistry at C4-C5. See the Supporting Information for details on the X-ray structure of enantiopure exo-4a. For the configuration of the endo isomer, it has been assumed that the endo/exo cycloaddition occurs with the same π-facial selectivity on the dipole-Cu complex (pyrrolidine adducts with 2S,5S configuration).
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For a previous example of aromatization of sulfonylpyrrolidines, see
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