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Intramolecular Oxypalladation
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Negishi, E.-I, Ed, John Wiley and Sons: New York
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(a) Hosokawa, T.; Murahashi, S.-I. Intramolecular Oxypalladation, In Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 2; Negishi, E.-I., Ed.; John Wiley and Sons: New York, 2002, 2169.
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For reviews, see: a, Negishi, E.-I, Ed, John Wiley and Sons: New York
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For reviews, see: (a) Tsuji, J. In Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 1; Negishi, E.-I., Ed.; John Wiley and Sons: New York, 2002, 1669.
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Tsuji, J.1
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Miyabe, H.; Yoshida, K.; Reddy, V. K.; Matsumura, A.; Takemoto, Y. J. Org. Chem. 2005, 70, 5630.
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Yoshida, K.2
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Miyabe, H.; Yoshida, K.; Yamauchi, M.; Takemoto, Y. J. Org. Chem. 2005, 70, 2148.
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18744403152
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Padwa, A, Ed, Georg Thieme Verlag: New York
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Merino, P. In Science of Synthesis, Vol. 27; Padwa, A., Ed.; Georg Thieme Verlag: New York, 2004, 511.
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Merino, P.1
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84995561494
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Attanasi, O. A, Spinelli, D, Eds, Italian Society of Chemistry: Rome
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Merino, P. In Targets in Heterocyclic Systems: Chemistry and Properties, Vol. 7; Attanasi, O. A.; Spinelli, D., Eds.; Italian Society of Chemistry: Rome, 2003, 140.
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, vol.7
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Merino, P.1
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34247120819
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To the best of our knowledge, the only precedent so far reported (see ref. 5) deals with intermolecular reactions, using carbonates as leaving groups, and necessitating an electron-withdrawing group on the hydroxylamine nitrogen atom
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To the best of our knowledge, the only precedent so far reported (see ref. 5) deals with intermolecular reactions, using carbonates as leaving groups, and necessitating an electron-withdrawing group on the hydroxylamine nitrogen atom.
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14
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33646468425
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(a) Merino, P.; Delso, I.; Mannucci, V.; Tejero, T. Tetrahedron Lett. 2006, 47, 3311.
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(2006)
Tetrahedron Lett
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Merino, P.1
Delso, I.2
Mannucci, V.3
Tejero, T.4
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15
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0035968986
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(b) Laskar, D. D.; Prajapati, D.; Sandhu, J. S. Tetrahedron Lett. 2001, 42, 7883.
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(2001)
Tetrahedron Lett
, vol.42
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Laskar, D.D.1
Prajapati, D.2
Sandhu, J.S.3
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16
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0034716015
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(c) Kumar, H. M. S.; Anjaneyulu, S.; Reddy, E. J.; Yadav, J. S. Tetrahedron Lett. 2000, 41, 9311.
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(2000)
Tetrahedron Lett
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Kumar, H.M.S.1
Anjaneyulu, S.2
Reddy, E.J.3
Yadav, J.S.4
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17
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14844300911
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Merino, P.; Mannucci, V.; Tejero, T. Tetrahedron 2005, 61, 3335.
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(2005)
Tetrahedron
, vol.61
, pp. 3335
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Merino, P.1
Mannucci, V.2
Tejero, T.3
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0034639441
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Alkene 5 has been successfully used in ruthenium-catalyzed cross-metathesis reactions. For representative examples, see: (a) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58.
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Alkene 5 has been successfully used in ruthenium-catalyzed cross-metathesis reactions. For representative examples, see: (a) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58.
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19
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0001754263
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(b) Chatterjee, A. K.; Sanders, D. P.; Grubbs, R. H. Org. Lett. 2002, 11, 1939.
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(2002)
Org. Lett
, vol.11
, pp. 1939
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Chatterjee, A.K.1
Sanders, D.P.2
Grubbs, R.H.3
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20
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0037720744
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(c) Chatterjee, A. K.; Toste, F. D.; Choi, T.-L.; Grubbs, R. H. Adv. Synth. Catal. 2002, 344, 634.
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(2002)
Adv. Synth. Catal
, vol.344
, pp. 634
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Chatterjee, A.K.1
Toste, F.D.2
Choi, T.-L.3
Grubbs, R.H.4
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21
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(d) Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360.
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(2003)
J. Am. Chem. Soc
, vol.125
, pp. 11360
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Chatterjee, A.K.1
Choi, T.-L.2
Sanders, D.P.3
Grubbs, R.H.4
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27744464923
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(e) Cluzeau, J.; Capdevielle, P.; Cossy, J. Tetrahedron Lett. 2005, 40, 6945.
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(2005)
Tetrahedron Lett
, vol.40
, pp. 6945
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Cluzeau, J.1
Capdevielle, P.2
Cossy, J.3
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23
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0033518572
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(a) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791.
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(1999)
J. Am. Chem. Soc
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Kingsbury, J.S.1
Harrity, J.P.A.2
Bonitatebus, P.J.3
Hoveyda, A.H.4
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24
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(b) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168.
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J. Am. Chem. Soc
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Garber, S.B.1
Kingsbury, J.S.2
Gray, B.L.3
Hoveyda, A.H.4
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25
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17844369291
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Murahashi, S.-I, Ed, Wiley-VCH: New York
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(c) Grubbs, R. H.; Trnka, T. M. In Ruthenium in Organic Synthesis; Murahashi, S.-I., Ed.; Wiley-VCH: New York, 2004, 153-177.
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(2004)
Ruthenium in Organic Synthesis
, pp. 153-177
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Grubbs, R.H.1
Trnka, T.M.2
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15044355873
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It has been recently described that the use of Lewis acids can prevent undesired coordination of N-atom to the ruthenium carbene intermediate in metathesis reactions: (a) Yang, Q, Xiao, W.-J, Yu, Z. Org. Lett. 2005, 7, 871
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It has been recently described that the use of Lewis acids can prevent undesired coordination of N-atom to the ruthenium carbene intermediate in metathesis reactions: (a) Yang, Q.; Xiao, W.-J.; Yu, Z. Org. Lett. 2005, 7, 871.
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34247129367
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Use of tert-butyldimethylsilyl chloride in the presence of several tertiary amines failed to give the corresponding protected hydroxylamine.
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Use of tert-butyldimethylsilyl chloride in the presence of several tertiary amines failed to give the corresponding protected hydroxylamine.
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34247127228
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Data for 6a: (90, Rf, 0.55 (hexane-EtOAc, 4:1, oil. 1H NMR (400 MHz, CDCl3, 25°C, mixture of conformers, δ, 7.27-7.22 (m, 3 H, 7.21-7.13 (m, 4 H, 7.04-6.98 (m, 3 H, 5.61-5.55 (m, 1.6 H, 5.54-5.43 (m, 0.4 H, 4.58-4.50 (m, 0.4 H, 4.41-4.37 (m, 1.6 H, 4.20 (t, 1 H, J, 7.5 Hz, 2.79 (t, 2 H, J, 6.7 Hz, 2.06 (br, 0.6 H, 2.02 (br, 2.4 H, 0.3 (br, 9 H, 0.07 (br, 3 H, 0.31 (br, 0.6 H, 0.34 (br, 2.4 H, 13C NMR 100 MHz, CDCl3, 25°C, selected signals for the major conformer, δ, 170.7, 152,5, 137.8, 133.3, 131.9, 127.9, 127.5, 127.4, 125.8, 123.7, 121.2, 74.3, 65.0, 32.9, 26.1, 21.0, 18.0, 4.7, 5.5. Anal Calcd for C25H 35NO3Si: C, 70.55; H, 8.29; N, 3.29. Found: C, 70.59; H, 8.45; N, 3.22
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3Si: C, 70.55; H, 8.29; N, 3.29. Found: C, 70.59; H, 8.45; N, 3.22.
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32
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0037039966
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(b) Lei, A.; Liu, G.; Lu, X. J. Org. Chem. 2002, 67, 974.
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(2002)
J. Org. Chem
, vol.67
, pp. 974
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Lei, A.1
Liu, G.2
Lu, X.3
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1642328126
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(c) Miyazawa, M.; Hirose, Y.; Narantsetseg, M.; Yokoyama, H.; Yamaguchi, S.; Hirai, Y. Tetrahedron Lett. 2004, 45, 2883.
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(2004)
Tetrahedron Lett
, vol.45
, pp. 2883
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Miyazawa, M.1
Hirose, Y.2
Narantsetseg, M.3
Yokoyama, H.4
Yamaguchi, S.5
Hirai, Y.6
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34
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0034632383
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(d) Yokoyama, H.; Otaya, K.; Kobayashi, H.; Miyazawa, M.; Yamaguchi, S.; Hirai, Y. Org. Lett. 2000, 2, 2427.
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(2000)
Org. Lett
, vol.2
, pp. 2427
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Yokoyama, H.1
Otaya, K.2
Kobayashi, H.3
Miyazawa, M.4
Yamaguchi, S.5
Hirai, Y.6
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35
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33748274686
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(e) Ferber, B.; Prestat, G.; Vogel, S.; Madec, D.; Poli, G. Synlett 2006, 2133.
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(2006)
Synlett
, pp. 2133
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Ferber, B.1
Prestat, G.2
Vogel, S.3
Madec, D.4
Poli, G.5
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36
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0038739205
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We recently reported a related comparative study of Pd(0) vs. nonoxidative Pd(II) catalysis for intramolecular allylic amination, see ref. 18e and: Ferber, B, Lemaire, S, Mader, M. M, Prestat, G, Poli, G. Tetrahedron Lett. 2003, 44, 4213
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We recently reported a related comparative study of Pd(0) vs. nonoxidative Pd(II) catalysis for intramolecular allylic amination, see ref. 18e and: Ferber, B.; Lemaire, S.; Mader, M. M.; Prestat, G.; Poli, G. Tetrahedron Lett. 2003, 44, 4213.
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37
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34247110208
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General Procedure for the Pd(0)-Mediated Intramolecular Allylic Alkylation The proper homoallylhydroxylamine (1 mmol) and (if needed) NaH (60% dispersion in a mineral oil, 1 mmol) were dissolved in DMF (20 mL) under an argon atmosphere and the resulting mixture was cooled to 0°C. In a separate flask, Pd(OAc)2 (5 mol, and dppe (10 mol, were mixed in DMF (5 mL) and stirred for ca 5 min. After having carefully verified that the initially brown solution turned into a paler brown suspension, the thus formed Pd(0) catalyst was added into the solution of hydroxylamine. The resulting mixture was stirred at r.t. for 30 min, then heated at 80°C for 3 h. After cooling to r.t, the solution was poured into Et2O (125 mL) and H2O (50 mL) was added. The organic layer was separated and the aqueous layer was extracted with Et2O. The combined organic extracts were washed with brine, dried over MgSO4, filtered and evaporated under re
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4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
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38
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34247096308
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4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
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4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
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39
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34247100019
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The relative stereochemical assignment of compound 8a was based on ROESY experiments.
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The relative stereochemical assignment of compound 8a was based on ROESY experiments.
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40
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0000151617
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2/phosphine is amply documented. See for example: (a) Amatore, C.; Carre, E.; Jutand, A.; M'Barke, M. A. Organometallics 1995, 14, 1818.
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2/phosphine is amply documented. See for example: (a) Amatore, C.; Carre, E.; Jutand, A.; M'Barke, M. A. Organometallics 1995, 14, 1818.
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41
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0035939692
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(b) Amatore, C.; Jutand, A.; Thuilliez, A. Organometallics 2001, 20, 3241.
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(2001)
Organometallics
, vol.20
, pp. 3241
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Amatore, C.1
Jutand, A.2
Thuilliez, A.3
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34247099550
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2, gave only starting material, thereby ruling out the possibility of a noncatalytic cyclization passing through the corresponding allylic bromide.
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2, gave only starting material, thereby ruling out the possibility of a noncatalytic cyclization passing through the corresponding allylic bromide.
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44
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34247167371
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Data for 10: Rf, 0.36 (hexane-EtOAc, 4:1, α]D20 +92 (c 0.16, CHCl3, 1H NMR (400 MHz, CDCl3, 25°C, δ, 7.45-7.40 (m, 2 H, 7.37-7.31 (m, 2 H, 7.30-7.24 (m, 1 H, 5.85 (ddd, 1 H, J, 17.2, 10.3, 7.1 Hz, 5.29 (d, 1 H, J, 17.2 Hz, 5.18 (d, 1 H, J, 10.3 Hz, 4.47 (dt, 1 H, J, 7.6, 7.1 Hz, 4.34 (d, 1 H, J, 14.0 Hz, 4.15 (dt, 1 H, J, 7.1, 6.5 Hz, 4.04 (dd, 1 H, J, 8.3, 6.5 Hz, 4.00 (d, 1 H, J, 14.0 Hz, 3.74 (dd, 1 H, J, 8.3, 7.1 Hz, 3.13 (dt, 1 H, J, 8.2, 7.1 Hz, 2.21-2.04 (m, 2 H, 1.44 (s, 3 H, 1.36 (s, 3 H, 13C NMR 100 MHz, CDCl3, 25°C, δ, 137.6, 137.2, 129.2, 128.2, 127.2, 117.5, 109.8, 78.4, 77.2, 67.2, 66.9, 62.2, 37.5, 26.7, 25.4. Anal. Calcd for C17H23NO3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.47; H, 8.13; N, 4.76
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3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.47; H, 8.13; N, 4.76.
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45
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34247141249
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Data for 12: Rf, 0.42 (hexane-EtOAc, 4:1, α]D20 +21 (c 1.38, CHCl3, 1H NMR (400 MHz, CDCl3, 25°C, δ, 7.31-7.17 (m, 5H, 5.89-5.79 (ddd, 1 H, J, 17.1, 10.2, 7.4 Hz, 5.20 (dt, 1 H, J, 17.1, 1.2 Hz, 5.10 (dt, 1 H, J, 10.2, 1.2 Hz, 4.50 (q, 1 H, J, 7.4 Hz, 4.04 (d, 1 H, J, 12.8 Hz, 3.98-3.92 (m, 2 H, 3.77 (d, 1 H, J, 12.8 Hz, 3.47-3.40 (m, 1 H, 3.16-3.10 (t, 1 H, J, 6.9 Hz, 2.48 (dddd, 1 H, J, 12.8, 9.2, 7.4, 1.6 Hz, 2.15 (ddd, 1 H, J, 12.8, 9.2, 7.4 Hz, 1.27 (s, 3 H, 1.24 (s, 3 H, 13C NMR 100 MHz, CDCl3, 25°C, δ, 138.2, 137.0, 129.3, 128.5, 127.6, 117.3, 109.3, 80.4, 75.7,68.0, 67.4, 63.6, 36.1, 26.8, 25.3. Anal. Calcd for C17H23NO3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.70; H, 7.88; N, 5.01
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3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.70; H, 7.88; N, 5.01.
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