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Volumn 129, Issue 23, 2007, Pages 7274-7276

syn-1,2-amino alcohols via diastereoselective allylic C-H amination

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID; ALKENE; ALLYL COMPOUND; AMINOALCOHOL; BENZOQUINONE; CARBAMIC ACID; CARBOXYLIC ACID; LACTACYSTIN; LEWIS BASE; OXAZOLIDINONE DERIVATIVE; PALLADIUM; RUTHENIUM; SYN 1,2 AMINO ALCOHOL; UNCLASSIFIED DRUG;

EID: 34250877913     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja071905g     Document Type: Article
Times cited : (308)

References (53)
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    • C-O to C-N catalyzed by Pd(0): (a) Trost, B. M.; Sudhakar, A. R. J. Am. Chem. Soc. 1987, 109, 3792.
    • C-O to C-N catalyzed by Pd(0): (a) Trost, B. M.; Sudhakar, A. R. J. Am. Chem. Soc. 1987, 109, 3792.
  • 8
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    • Olefin aminohydroxylation: (h) Kolb, H. C.; Sharpless, K. B. In Transition Metals for Organic Synthesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH Verlag: Weinheim, Germany, 2004; p 309. Mannich:
    • Olefin aminohydroxylation: (h) Kolb, H. C.; Sharpless, K. B. In Transition Metals for Organic Synthesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH Verlag: Weinheim, Germany, 2004; p 309. Mannich:
  • 12
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    • Streamlining syntheses via late stage C-H oxidation see: a
    • Streamlining syntheses via late stage C-H oxidation see: (a) Fraunhoffer, K. J.; Bachovchin, D. A.; White, M. C. Org. Lett. 2005, 7, 223.
    • (2005) Org. Lett , vol.7 , pp. 223
    • Fraunhoffer, K.J.1    Bachovchin, D.A.2    White, M.C.3
  • 15
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    • Elegant examples of late stage C-H hydroxylation and amination see: d
    • Elegant examples of late stage C-H hydroxylation and amination see: (d) Wender, P. A.; Hilinski, M. K.; Mayweg, A. V. W. Org. Lett. 2005, 7, 79.
    • (2005) Org. Lett , vol.7 , pp. 79
    • Wender, P.A.1    Hilinski, M.K.2    Mayweg, A.V.W.3
  • 17
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    • C-H amination via metal nitrenes: (a) Espino, C. G.; Du Bois, J. Angew. Chem., Int. Ed. 2001, 40, 598.
    • C-H amination via metal nitrenes: (a) Espino, C. G.; Du Bois, J. Angew. Chem., Int. Ed. 2001, 40, 598.
  • 20
    • 34250887994 scopus 로고    scopus 로고
    • For single examples of catalytic allylic C-H amination: (a) ref 3b.
    • For single examples of catalytic allylic C-H amination: (a) ref 3b.
  • 24
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    • ref. 4b
    • (c) ref. 4b.
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    • and references therein
    • (b) Trost, B. M. Tetrahedron 1977, 33, 2615 and references therein.
    • (1977) Tetrahedron , vol.33 , pp. 2615
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  • 39
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    • 2O) of EtOC(O)NHTs = 3.7. Taylor, L. D.; Pluhar, M.; Rubin, L. E. J. Polym. Sci., Part B: Polym. Phys. 1967, 5, 77.
    • 2O) of EtOC(O)NHTs = 3.7. Taylor, L. D.; Pluhar, M.; Rubin, L. E. J. Polym. Sci., Part B: Polym. Phys. 1967, 5, 77.
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    • 2. Only ca. 1% of the allylic acetate product observed (Supporting Information, SI-23).
    • 2. Only ca. 1% of the allylic acetate product observed (Supporting Information, SI-23).
  • 41
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    • 3, and -OC(O)NH(p-OMe)Ph with less acidic N-H bonds showed poor reactivities. Addition of 10 mol% Hunig's base to p-anisyl carbamate substrate gave no significant improvement (SI-9 and ref 24).
    • 3, and -OC(O)NH(p-OMe)Ph with less acidic N-H bonds showed poor reactivities. Addition of 10 mol% Hunig's base to p-anisyl carbamate substrate gave no significant improvement (SI-9 and ref 24).
  • 42
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    • 1,1-disubstituted and 1,2-disubstituted olefin substrates proceeded with poor conversions (30%) and yields (ca. 8-12% as mixtures of oxidative amination products), (b) Methyl 2-(tosylcarbamoyloxy)pent-4-enoate gave a complex mixture of products (ca. 30% anti-oxazolidinone identified) (SI-8,9).
    • (a) 1,1-disubstituted and 1,2-disubstituted olefin substrates proceeded with poor conversions (30%) and yields (ca. 8-12% as mixtures of oxidative amination products), (b) Methyl 2-(tosylcarbamoyloxy)pent-4-enoate gave a complex mixture of products (ca. 30% anti-oxazolidinone identified) (SI-8,9).
  • 45
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    • For alternative syntheses see
    • For alternative syntheses see: Bonini, C.; Righi, G. Tetrahedron 2002, 58, 4981.
    • (2002) Tetrahedron , vol.58 , pp. 4981
    • Bonini, C.1    Righi, G.2
  • 48
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    • Unlike allylic C-H oxidation, Pd/sulfoxide-catalyzed allylic C-H amination does not require quinone for functionalization and therefore does not proceed via a serial ligand catalysis mechanism. See ref 10a
    • Unlike allylic C-H oxidation, Pd/sulfoxide-catalyzed allylic C-H amination does not require quinone for functionalization and therefore does not proceed via a serial ligand catalysis mechanism. See ref 10a.
  • 50
    • 34250869414 scopus 로고    scopus 로고
    • 1H NMR monitoring at 5, 24, 48, and 72 h (signal/noise > 500:1) (SI-24). The possibility that trace levels of 17 and/or 18 form under standard reaction conditions and contribute to formation of 3a cannot be rigorously excluded.
    • 1H NMR monitoring at 5, 24, 48, and 72 h (signal/noise > 500:1) (SI-24). The possibility that trace levels of 17 and/or 18 form under standard reaction conditions and contribute to formation of 3a cannot be rigorously excluded.
  • 51
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    • Previous work (ref 1a and ref 1b) in Pd(0)-mediated allylic substitution reactions has shown that the poor nucleophilic properties of carbamates require the use of their respective anions to achieve reactivity with π-allylpalladium intermediates.
    • Previous work (ref 1a and ref 1b) in Pd(0)-mediated allylic substitution reactions has shown that the poor nucleophilic properties of carbamates require the use of their respective anions to achieve reactivity with π-allylpalladium intermediates.
  • 53
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    • For an alternative-approach to this see
    • For an alternative-approach to this see: Lafrance, M.; Fagnou, K. J. Am. Chem. Soc 2006, 128, 16496.
    • (2006) J. Am. Chem. Soc , vol.128 , pp. 16496
    • Lafrance, M.1    Fagnou, K.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.