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Ortho-metalation reactions of aromatic aldehydes by n-BuLi in the presence of lithium dialkylamides: (a) Comins, D. L; Brown, J. D. J. Org. Chem. 1984, 48, 1937.
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85069256801
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In a recent publication, we put forward for consideration that in the crucial step of the lithiation reaction, the directing and accelerating effect of the substituents might be due to the stabilization of both the initial complex and the transition structure (respectively 7 and 8 in this work, Coordination might be stronger in the transition state than in the initial complex. As a result, complexation would increase the rate of the reaction by providing a new mechanism that has a smaller activation energy Ea, See ref. 21d
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a). See ref. 21d.
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21
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85022954422
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3 could allow the formation of a dianion. See: Svensson, A.; Martin, A. Heterocycles 1985, 23, 357.
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3 could allow the formation of a dianion. See: Svensson, A.; Martin, A. Heterocycles 1985, 23, 357.
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22
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0016052105
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An analogous anionic N → C migration of arylsulfonamides has been reported: (a) Hellwinkel, D, Supp, M. Angew. Chem, Int. Ed. 1970, 13, 270
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An analogous anionic N → C migration of arylsulfonamides has been reported: (a) Hellwinkel, D.; Supp, M. Angew. Chem., Int. Ed. 1970, 13, 270.
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25
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Hallberg, A.; Dunbar, P.; Hintermeister, N. M.; Svensson, A.; Martin, A. R. J. Chem. Soc., Perkin Trans. 1 1985, 969.
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26
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85069253264
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2OLi group cannot be metalated further and acid hydrolysis leads to an α-aminoalcohol that decomposes to give 1 and formaldehyde. The implication of a diacetylated species (by reaction of 10 with a second molecule of RCOX) on the reaction coordinate to explain the formation of 4a-d can be ruled out since only one equivalent of amide is required to give a high yield of 4a-d. See ref. 5a.
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2OLi group cannot be metalated further and acid hydrolysis leads to an α-aminoalcohol that decomposes to give 1 and formaldehyde. The implication of a diacetylated species (by reaction of 10 with a second molecule of RCOX) on the reaction coordinate to explain the formation of 4a-d can be ruled out since only one equivalent of amide is required to give a high yield of 4a-d. See ref. 5a.
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27
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85069244981
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Tilly, D.; Samanta, S. S.; De, A.; Castanet, A.-S.; Mortier, J. Org. Lett. 2005, 7, 827. 16.
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(d) Katritzky, A. R.; Black, M.; Fan, W.-Q. J. Org. Chem. 1991, 55, 5045.
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32
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85069244858
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methylformanilide are rapidly deprotonated under these conditions
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N-Methylacetanilide and N-methylformanilide are rapidly deprotonated under these conditions.
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N-Methylacetanilide and N
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35
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Gohier, F.; Castanet, A.-S.; Mortier, J. J. Org. Chem. 2005, 70, 1501.
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For recent work on ortho-lithiation reactions of unprotected benzoic acid derivatives, see: (a) Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids: Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919.
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For recent work on ortho-lithiation reactions of unprotected benzoic acid derivatives, see: (a) Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids: Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919.
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39
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0037424307
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Ortho-lithiation of unprotected 3-bromo and 3-chlorobenzoic acids with hindered bases: Gohier, F.; Mortier, J. J. Org. Chem. 2003, 68, 2030.
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(b) Ortho-lithiation of unprotected 3-bromo and 3-chlorobenzoic acids with hindered bases: Gohier, F.; Mortier, J. J. Org. Chem. 2003, 68, 2030.
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40
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19444387314
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Reactions of unprotected naphthalene-1-carboxylic acid with strong bases: Tilly, D.; Castanet, A.-S.; Mortier, J. Chem. Lett. 2005, 34, 446.
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(c) Reactions of unprotected naphthalene-1-carboxylic acid with strong bases: Tilly, D.; Castanet, A.-S.; Mortier, J. Chem. Lett. 2005, 34, 446.
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41
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20544457346
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Mechanism of ortholithiation. Tuning of selectivities in the metalation of meta-anisic acid: Nguyen, T. H.; Chau, N. T. T.; Castanet, A.-S.; Nguyen, K. P. P.; Mortier, J. Org. Lett. 2005, 7, 2445.
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(d) Mechanism of ortholithiation. Tuning of selectivities in the metalation of meta-anisic acid: Nguyen, T. H.; Chau, N. T. T.; Castanet, A.-S.; Nguyen, K. P. P.; Mortier, J. Org. Lett. 2005, 7, 2445.
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42
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15944406848
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Novel 6-substituted-2-chlorobenzoic acid syntheses: Gohier, F.; Castanet, A.-S.; Mortier, J. Synth. Commun. 2005, 35, 799.
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(e) Novel 6-substituted-2-chlorobenzoic acid syntheses: Gohier, F.; Castanet, A.-S.; Mortier, J. Synth. Commun. 2005, 35, 799.
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43
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33644752654
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Regioselective synthesis of contiguously 3- and 6-substituted 2-methoxybenzoic acid building blocks: Nguyen, T. H.; Castanet, A.-S.; Mortier, J. Org. Lett. 2006, 8, 765.
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(f) Regioselective synthesis of contiguously 3- and 6-substituted 2-methoxybenzoic acid building blocks: Nguyen, T. H.; Castanet, A.-S.; Mortier, J. Org. Lett. 2006, 8, 765.
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44
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30544432154
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On the mechanism of the metalation of 2-(pyridin-3-yl)benzoic acid derivatives: Tilly, D.; Castanet, A.-S.; Mortier, J. Tetrahedron Lett. 2006, 47, 1121.
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(g) On the mechanism of the metalation of 2-(pyridin-3-yl)benzoic acid derivatives: Tilly, D.; Castanet, A.-S.; Mortier, J. Tetrahedron Lett. 2006, 47, 1121.
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34547904032
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Regioselective metalation of unprotected 2-, 3- and 4-biphenylcarboxylic acids: Tilly, D.; Samanta, S. S.; Castanet, A.-S.; De, A.; Mortier, J. Eur. J. Org. Chem. 2006, 174.
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(h) Regioselective metalation of unprotected 2-, 3- and 4-biphenylcarboxylic acids: Tilly, D.; Samanta, S. S.; Castanet, A.-S.; De, A.; Mortier, J. Eur. J. Org. Chem. 2006, 174.
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