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For reactions employing Eaton's reagent, refer to: (a) Eaton, P. E.; Carlson, G. R.; Lee, J. T. J. Org. Chem. 1973, 38, 4071-4073.
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For reactions employing Eaton's reagent, refer to: (a) Eaton, P. E.; Carlson, G. R.; Lee, J. T. J. Org. Chem. 1973, 38, 4071-4073.
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16
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Trost, B.M.1
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17
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33745753488
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During the preparation of this manuscript, a similar transformation of an o-iodoaniline intermediate at 90°C using Eaton's reagent was reported: Dorow, R. L.; Herrinton, P. M.; Hohler, R. A.; Maloney, M. T.; Mauragis, M. A.; McGhee, W. E.; Moeslein, J. A.; Strohbach, J. W.; Veley, M. F. Org. Process Res. Dev. 2006, 10, 493-499.
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(d) During the preparation of this manuscript, a similar transformation of an o-iodoaniline intermediate at 90°C using Eaton's reagent was reported: Dorow, R. L.; Herrinton, P. M.; Hohler, R. A.; Maloney, M. T.; Mauragis, M. A.; McGhee, W. E.; Moeslein, J. A.; Strohbach, J. W.; Veley, M. F. Org. Process Res. Dev. 2006, 10, 493-499.
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18
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34249776535
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3H) was purchased from Sigma-Aldrich
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3H) was purchased from Sigma-Aldrich
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19
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46149138072
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Gradient 1D NOESY using Gaussian excitation pulse and 500-600 ms mixing time: (a) Kessler, H.; Oschkinat, H.; Griesinger, C.; Bermel, W. J. J. Magn. Reson. 1986, 70, 106-133.
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Gradient 1D NOESY using Gaussian excitation pulse and 500-600 ms mixing time: (a) Kessler, H.; Oschkinat, H.; Griesinger, C.; Bermel, W. J. J. Magn. Reson. 1986, 70, 106-133.
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20
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0000334646
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21
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0000445956
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NOE summary
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(c) Stott, K.; Stonehouse, J.; Keeler, J.; Hwang, T. L.; Shaka, A. J. J. Am. Chem. Soc. 1995, 117, 4199-4200. NOE summary:
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(a) Lew, A.; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95-105.
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Lew, A.1
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23
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34249815675
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Microwave-assisted synthesis of 1b was briefly explored and found to give product, albeit in poor yields.
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(b) Microwave-assisted synthesis of 1b was briefly explored and found to give product, albeit in poor yields.
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24
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34249788591
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4, TFA, or HOAc at 50-100°C over prolonged period of time resulted in the recovery of substrate 1a along with significant amounts of hydrolysis product (aniline).
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4, TFA, or HOAc at 50-100°C over prolonged period of time resulted in the recovery of substrate 1a along with significant amounts of hydrolysis product (aniline).
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25
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34249782153
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The use of 1:1 and 2:1 mixtures of solvents including toluene, xylene, and tetramethylene sulfone along with Eaton's reagent resulted in sluggish conversion. The best conversion obtained was 3% after 20 h at 100°C in a 1:1 mixture of toluene and Eaton's reagent.
-
The use of 1:1 and 2:1 mixtures of solvents including toluene, xylene, and tetramethylene sulfone along with Eaton's reagent resulted in sluggish conversion. The best conversion obtained was 3% after 20 h at 100°C in a 1:1 mixture of toluene and Eaton's reagent.
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26
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34249828385
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See the Experimental Section
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See the Experimental Section.
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27
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0035821423
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33
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34249793866
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Aryl amines with electron donating as well as withdrawing substituents at the meta position resulted in messy reaction profiles. An attempt to synthesize 1,4-dihydro-7-methoxy-4-oxo-2-quinolonecarboxylic acid, methyl ester from a substrate that was derived from O-methoxyaniline afforded only 30% of one major cyclized product with several unidentified side products LC/MS studies
-
Aryl amines with electron donating as well as withdrawing substituents at the meta position resulted in messy reaction profiles. An attempt to synthesize 1,4-dihydro-7-methoxy-4-oxo-2-quinolonecarboxylic acid, methyl ester from a substrate that was derived from O-methoxyaniline afforded only 30% of one major cyclized product with several unidentified side products (LC/MS studies).
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36
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34249829484
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2 substituent was only 3% over the same period.
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2 substituent was only 3% over the same period.
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