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Volumn , Issue 6, 2007, Pages 944-948

Hydroxylamine oxygen as nucleophile in palladium(0)- and palladium(II)-catalyzed allylic alkylation: A novel access to isoxazolidines

Author keywords

Allyl complexes; Hydroxylamines; Isoxazolidines; Palladium; Ring closure

Indexed keywords

5 VINYL ISOXAZOLIDINE; ALLYL COMPOUND; HYDROXYLAMINE; ISOXAZOLIDINE DERIVATIVE; OXYGEN; PALLADIUM COMPLEX; UNCLASSIFIED DRUG;

EID: 34247096022     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-973868     Document Type: Article
Times cited : (13)

References (45)
  • 5
  • 11
    • 18744403152 scopus 로고    scopus 로고
    • Padwa, A, Ed, Georg Thieme Verlag: New York
    • Merino, P. In Science of Synthesis, Vol. 27; Padwa, A., Ed.; Georg Thieme Verlag: New York, 2004, 511.
    • (2004) Science of Synthesis , vol.27 , pp. 511
    • Merino, P.1
  • 12
  • 13
    • 34247120819 scopus 로고    scopus 로고
    • 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
    • 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.
  • 18
    • 0034639441 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 26
    • 15044355873 scopus 로고    scopus 로고
    • 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
    • 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.
  • 28
    • 34247129367 scopus 로고    scopus 로고
    • Use of tert-butyldimethylsilyl chloride in the presence of several tertiary amines failed to give the corresponding protected hydroxylamine.
    • Use of tert-butyldimethylsilyl chloride in the presence of several tertiary amines failed to give the corresponding protected hydroxylamine.
  • 29
    • 34247127228 scopus 로고    scopus 로고
    • 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
    • 3Si: C, 70.55; H, 8.29; N, 3.29. Found: C, 70.59; H, 8.45; N, 3.22.
  • 36
    • 0038739205 scopus 로고    scopus 로고
    • 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
    • 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.
  • 37
    • 34247110208 scopus 로고    scopus 로고
    • 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
    • 4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
  • 38
    • 34247096308 scopus 로고    scopus 로고
    • 4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
    • 4, filtered and evaporated under reduced pressure to give a residue which was purified by radial chromatography.
  • 39
    • 34247100019 scopus 로고    scopus 로고
    • The relative stereochemical assignment of compound 8a was based on ROESY experiments.
    • The relative stereochemical assignment of compound 8a was based on ROESY experiments.
  • 40
    • 0000151617 scopus 로고    scopus 로고
    • 2/phosphine is amply documented. See for example: (a) Amatore, C.; Carre, E.; Jutand, A.; M'Barke, M. A. Organometallics 1995, 14, 1818.
    • 2/phosphine is amply documented. See for example: (a) Amatore, C.; Carre, E.; Jutand, A.; M'Barke, M. A. Organometallics 1995, 14, 1818.
  • 43
    • 34247099550 scopus 로고    scopus 로고
    • 2, gave only starting material, thereby ruling out the possibility of a noncatalytic cyclization passing through the corresponding allylic bromide.
    • 2, gave only starting material, thereby ruling out the possibility of a noncatalytic cyclization passing through the corresponding allylic bromide.
  • 44
    • 34247167371 scopus 로고    scopus 로고
    • 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
    • 3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.47; H, 8.13; N, 4.76.
  • 45
    • 34247141249 scopus 로고    scopus 로고
    • 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
    • 3: C, 70.56; H, 8.01; N, 4.84. Found: C, 70.70; H, 7.88; N, 5.01.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.