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b) P. Merino, J. A. Mates, J. Revuelta, T. Tejero, U. Chiacchio, G. Romeo, D. Iannazzo, R. Romeo, Tetrahedron: Asymmetry 2002, 13, 173-190.
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73
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2742535532
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For a similar use of the dioxolane ring in the synthesis of 4-oxopipecolic acids, see
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For a similar use of the dioxolane ring in the synthesis of 4-oxopipecolic acids, see: G. Galley, B. Ziemer, M. Pätzel, J. Prakt. Chem. 1998, 340, 551-556.
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Galley, G.1
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74
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85034386795
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For the enantiodivergent synthesis of α-amino acids through stereocontrolled Grignard nucleophilic additions to 10 following the same principle, see: P. Merino, E. Castillo, S. Franco, F. L. Merchan, T. Tejero, J. Org. Chem. 1998, 63, 2371-2374
-
For the enantiodivergent synthesis of α-amino acids through stereocontrolled Grignard nucleophilic additions to 10 following the same principle, see: P. Merino, E. Castillo, S. Franco, F. L. Merchan, T. Tejero, J. Org. Chem. 1998, 63, 2371-2374.
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75
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27944492745
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For reviews on allylation of imines and related compounds, see: a
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For reviews on allylation of imines and related compounds, see: a) H. Ding, G. K. Friestad, Synthesis 2005, 2815-2829;
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Ding, H.1
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33646469171
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b) P. Merino, T. Tejero, I. Delso, V. Mannucci, Curr. Org. Synth. 2005, 2, 479-498.
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Curr. Org. Synth
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Merino, P.1
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78
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0006130655
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D. Seyferth, M. A. Weiner, Org. Synth., Collect. 1973, 5, 452-455.
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Seyferth, D.1
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79
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84986703419
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The reaction of allylmagnesium bromide with 10 has been described previously. However, only the direct allylation was reported and an almost equimolar mixture of syn- and anti-13b was obtained: D. D. Dhavale, L. Gentilucci, M. G. Piazza, C. Trombini, Liebigs Ann. Chem. 1992, 1289-1295.
-
The reaction of allylmagnesium bromide with 10 has been described previously. However, only the direct allylation was reported and an almost equimolar mixture of syn- and anti-13b was obtained: D. D. Dhavale, L. Gentilucci, M. G. Piazza, C. Trombini, Liebigs Ann. Chem. 1992, 1289-1295.
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80
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53849125346
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When the reactions were carried out on the 10-20 mmol scale, the solution of precomplexed nitrone was precooled to -50 °C and added slowly by cannula to the cooled solution of allylmagnesium bromide.
-
When the reactions were carried out on the 10-20 mmol scale, the solution of precomplexed nitrone was precooled to -50 °C and added slowly by cannula to the cooled solution of allylmagnesium bromide.
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81
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R. Badorrey, C. Cativiela, M. D. Diaz-de-Villegas, R. Diez, J. A. Galvez, Eur. J. Org. Chem. 2002, 3763-3767.
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82
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34247096022
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Homoallyl hydroxylamines 8a and 8b have also been employed for the synthesis of vinyl isoxazolidines in a novel Pd-catalyzed heterocyclization procedure, see: P. Merino, T. Tejero, V. Mannucci, G. Prestat, D. Madec, G. Poli, Synlett 2007, 944-948.
-
Homoallyl hydroxylamines 8a and 8b have also been employed for the synthesis of vinyl isoxazolidines in a novel Pd-catalyzed heterocyclization procedure, see: P. Merino, T. Tejero, V. Mannucci, G. Prestat, D. Madec, G. Poli, Synlett 2007, 944-948.
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83
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A. Dondoni, S. Franco, F. L. Merchan, P. Merino, T. Tejero, Tetrahedron Lett. 1992, 33, 5475-5478.
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[35b] [47] a M. N. Paddon-Row, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1982, 104, 7162-7166;
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[35b] [47] a) M. N. Paddon-Row, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1982, 104, 7162-7166;
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0033873104
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This reaction has been described previously for nitrones to provide free hydroxylamines. For selected examples, see: a H. Tokuyama, T. Kuboyama, A. Amano, T. Yamashita, T. Fukuyama, Synthesis 2000, 1299-1304;
-
This reaction has been described previously for nitrones to provide free hydroxylamines. For selected examples, see: a) H. Tokuyama, T. Kuboyama, A. Amano, T. Yamashita, T. Fukuyama, Synthesis 2000, 1299-1304;
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89
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the same type of reaction has been reported using ionic liquids: d D. Li, F. Shi, S. Guo, Y. Deng, Tetrahedron Lett. 2004, 45, 265-268.
-
the same type of reaction has been reported using ionic liquids: d) D. Li, F. Shi, S. Guo, Y. Deng, Tetrahedron Lett. 2004, 45, 265-268.
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92
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33846649589
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For recent examples, see: a
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For recent examples, see: a) T. K. M. Shing, W. F. Wong, T. Ikeno, T. Yamada, Org. Lett. 2007, 9, 207-209;
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d) P. Padar, M. Hornyak, M. Forgo, Z. Kele, G. Paragi, N. M. Howarth, L. Kovacs, Tetrahedron 2005, 61, 6816-6823;
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For theoretical studies on the E/Z isomerization of C-alkoxycarbonyl and C-hetaryl nitrones, see: a P. Merino, J. Revuelta, T. Tejero, U. Chiacchio, A. Rescifina, G. Romeo, Tetrahedron 2003, 59, 3581-3592;
-
For theoretical studies on the E/Z isomerization of C-alkoxycarbonyl and C-hetaryl nitrones, see: a) P. Merino, J. Revuelta, T. Tejero, U. Chiacchio, A. Rescifina, G. Romeo, Tetrahedron 2003, 59, 3581-3592;
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99
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33845695224
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P. Merino, T. Tejero, U. Chiacchio, G. Romeo, A. Rescifina, Tetrahedron 2007, 63, 1448-1458. Another theoretical study on the mechanism of the E/Z isomerization of nitrones is underway in our laboratories.
-
b) P. Merino, T. Tejero, U. Chiacchio, G. Romeo, A. Rescifina, Tetrahedron 2007, 63, 1448-1458. Another theoretical study on the mechanism of the E/Z isomerization of nitrones is underway in our laboratories.
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100
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0028344826
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The E/Z isomerization of nitrones has been invoked by several authors to explain the products obtained, see: a M. T. Rispens, E. Keller, B. de Lange, R. W. J. Zijlstra, B. L. Feringa, Tetrahedron: Asymmetry 1994, 5, 607-615;
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The E/Z isomerization of nitrones has been invoked by several authors to explain the products obtained, see: a) M. T. Rispens, E. Keller, B. de Lange, R. W. J. Zijlstra, B. L. Feringa, Tetrahedron: Asymmetry 1994, 5, 607-615;
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101
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b) P. Merino, J. Revuelta, T. Tejero, U. Chiacchio, A. Rescifina, G. Romeo, Tetrahedron 2003, 59, 3581-3592.
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102
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For a complete analysis of all the possible adducts that could be formed, considering all the possibilities of epimerization, isomerization and rearrangement see the Supporting Information
-
For a complete analysis of all the possible adducts that could be formed, considering all the possibilities of epimerization, isomerization and rearrangement see the Supporting Information.
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-
-
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103
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33845471185
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For reviews on aza-Cope rearrangements, see: a
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b) A. Varlamov, V. Kouznetsov, F. Zubkov, A. Chernyshev, O. Shurupova, L. Y. V. Mendez, A. P. Rodriguez, J. R. Castro, A. J. Rojas-Romero, Synthesis 2002, 771-783.
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P. Merino, T. Tejero, V. Mannucci, Tetrahedron Lett. 2007, 48, 3385-3388. A complete theoretical study of thermal 2-aza-Cope rearrangement of nitrones is underway in our laboratory and will be reported in due course.
-
P. Merino, T. Tejero, V. Mannucci, Tetrahedron Lett. 2007, 48, 3385-3388. A complete theoretical study of thermal 2-aza-Cope rearrangement of nitrones is underway in our laboratory and will be reported in due course.
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112
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Analyses were performed by comparison of the HPLC chromatograms of the corresponding isolated reaction mixtures
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Analyses were performed by comparison of the HPLC chromatograms of the corresponding isolated reaction mixtures.
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113
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0036827950
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These conditions, however, have been reported for the O-silylation of 4-hydroxypiperidines, ee: M. K. S. Vink, C. A. Schortinghuis, J. Luten, J. H. van Maarseeven, H. E. Shoemaker, H. Hiemstra, F. P. J. T. Rutjes, J. Org. Chem. 2002, 67, 7869-7871.
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These conditions, however, have been reported for the O-silylation of 4-hydroxypiperidines, ee: M. K. S. Vink, C. A. Schortinghuis, J. Luten, J. H. van Maarseeven, H. E. Shoemaker, H. Hiemstra, F. P. J. T. Rutjes, J. Org. Chem. 2002, 67, 7869-7871.
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115
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53849123223
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A number of different conditions for introducing the Boc group were assayed with both 32 and 33. In the case of 32, unreacted starting compound was recovered in all cases.
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A number of different conditions for introducing the Boc group were assayed with both 32 and 33. In the case of 32, unreacted starting compound was recovered in all cases.
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