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for examples of the 3-aminotetrahydrofuran motif in synthesis, see: a
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for examples of the 3-aminotetrahydrofuran motif in synthesis, see: a) K. Oscarsson, M. Lahmann, J. Lindberg, J. Kangasmetsa, T. Unge, S. Oscarson, A. Hallberg, B. Samuelsson, Bioorg. Med. Chem. 2003, 11, 1107-1115;
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34547466737
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β-Hydride elimination remained competitive under all reaction conditions examined
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β-Hydride elimination remained competitive under all reaction conditions examined.
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31
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The modest yield of 2a was due to competitive formation of 2b and competitive decomposition of alcohol 2 to an intractable mixture of oxidation products.
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The modest yield of 2a was due to competitive formation of 2b and competitive decomposition of alcohol 2 to an intractable mixture of oxidation products.
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32
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34547463668
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2 is likely to act as a Lewis acid catalyst for this cyclization rather than to promote a rare 5-endo-trig oxypalladation/acetoxylation sequence.
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2 is likely to act as a Lewis acid catalyst for this cyclization rather than to promote a rare 5-endo-trig oxypalladation/acetoxylation sequence.
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33
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34547428506
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4 remains to be definitively elucidated. We speculate that it may render the Pd center more electrophilic and thereby promote coordination of the alcohol.
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4 remains to be definitively elucidated. We speculate that it may render the Pd center more electrophilic and thereby promote coordination of the alcohol.
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34
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48349088308
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For a rare example of 5-endo-trig oxypalladation, see: S. Saito, T. Hara, N. Takahashi, M. Hirai, T. Moriwake, Synlett 1992, 237-238.
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For a rare example of 5-endo-trig oxypalladation, see: S. Saito, T. Hara, N. Takahashi, M. Hirai, T. Moriwake, Synlett 1992, 237-238.
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35
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34547478775
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2.
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2.
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36
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34547489510
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(E)-3 did not form any THF product under these conditions; therefore, the stereochemical outcome of reactions with (Z)-3 appears to reflect a stereospecific transformation of the Z isomer and not isomerization to (E)-3 with subsequent aminocyclization.
-
(E)-3 did not form any THF product under these conditions; therefore, the stereochemical outcome of reactions with (Z)-3 appears to reflect a stereospecific transformation of the Z isomer and not isomerization to (E)-3 with subsequent aminocyclization.
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37
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34547430034
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The low yield of 3b appears to be due to fast catalyst decomposition under these conditions. The remainder of the material is predominantly (ca. 72%) a mixture of E and Z isomers of 3. See the Supporting Information for a full discussion.
-
The low yield of 3b appears to be due to fast catalyst decomposition under these conditions. The remainder of the material is predominantly (ca. 72%) a mixture of E and Z isomers of 3. See the Supporting Information for a full discussion.
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38
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For rare examples of cis aminopalladation, see reference [3a] and: a J. E. Ney, J. P. Wolfe, Angew. Chem. 2004, 116, 3689-3692;
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For rare examples of cis aminopalladation, see reference [3a] and: a) J. E. Ney, J. P. Wolfe, Angew. Chem. 2004, 116, 3689-3692;
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Retention of configuration has been observed in some Pd-catalyzed oxidative transformations with CuCl2; for example, see: G. Zhu, S. Ma, X. Lu, Q. Huang, J. Chem. Soc. Chem. Commun. 1995, 271-273
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2; for example, see: G. Zhu, S. Ma, X. Lu, Q. Huang, J. Chem. Soc. Chem. Commun. 1995, 271-273.
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42
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0000517091
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For examples of oxidative C-O bond formation at Pd that proceed with inversion, see: a J. E. Bäckvall, E. E. Bjoerkman, J. Org. Chem. 1980, 45, 2893-2898;
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For examples of oxidative C-O bond formation at Pd that proceed with inversion, see: a) J. E. Bäckvall, E. E. Bjoerkman, J. Org. Chem. 1980, 45, 2893-2898;
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