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Volumn 131, Issue 31, 2009, Pages 10875-10877

Enantioselective α-trifluoromethylation of aldehydes via photoredox organocatalysis

Author keywords

[No Author keywords available]

Indexed keywords

BUILDING BLOCKES; CHEMICAL EQUATIONS; ENANTIOSELECTIVE; HIGH EFFICIENCY; ORGANOCATALYSIS; ORGANOCATALYTIC; PERFLUOROALKYLATION; TRIFLUOROMETHYL; TRIFLUOROMETHYLATION;

EID: 68249144236     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9053338     Document Type: Article
Times cited : (878)

References (47)
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    • For seminal contributions towards the electrophilic or radical trifluoromethylation of enamines, enolates, and other carbonyl derivatives, see: (a) Cantacuzène, D.; Dorme, R. Tetrahedron Lett. 1975, 16, 2031-2034.
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    • For examples of moderately stereoselective methods, see: (a) Kitazume, T.; Ishikawa, N. J. Am. Chem. Soc. 1985, 107, 5186-5191.
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    • For recent examples of photoredox catalysis applications in organic synthesis, see: (a) Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2008, 130, 12886-12887.
    • (2008) J. Am. Chem. Soc , vol.130 , pp. 12886-12887
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    • Although Ir(ppy)2(dtb-bpy)PF6 1 was optimal for this transformation, commercially available Ru(bpy)3Cl 2 could also be used to afford the desired products in slightly diminished yields and enantioselectivities (Table 1, entry 5, 1 is available in a single step from commercially available [Ir(ppy) 2Cl]2 Sigma-Aldrich, CAS-No 92220-65-0, See ref 12
    • 2 (Sigma-Aldrich, CAS-No 92220-65-0). See ref 12.
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    • 6, Stern-Volmer constant = 185; see Supporting Information for details.
    • 6, Stern-Volmer constant = 185; see Supporting Information for details.
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    • Performed using B3LYP/6-311+G(2d,p)//B3LYP/6-31Gd, See ref 9
    • Performed using B3LYP/6-311+G(2d,p)//B3LYP/6-31G(d). See ref 9.
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    • We have recently shown the disruption of a postreaction racemization pathway via design of catalyst 2 versus catalyst 10, see: Amatore, M, Beeson, T. D, Brown, S. P, MacMillan, D. W. C. Angew. Chem, Int. Ed. 2009, 48, 5121-5124
    • We have recently shown the disruption of a postreaction racemization pathway via design of catalyst 2 (versus catalyst 10); see: Amatore, M.; Beeson, T. D.; Brown, S. P.; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2009, 48, 5121-5124.
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    • 3 formyl adduct was observed at room temperature but not at -20°C.
    • 3 formyl adduct was observed at room temperature but not at -20°C.
  • 44
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    • Lower reaction efficiency appears to lead to lower enantiopurity as the product is exposed to unconsumed base i.e, Table 1, entry 5, catalyst 9
    • Lower reaction efficiency appears to lead to lower enantiopurity as the product is exposed to unconsumed base (i.e., Table 1, entry 5, catalyst 9).
  • 45
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    • A hitherto unreported amine catalyst 11 was employed in entry 7 (Table 2); see Supporting Information.
    • A hitherto unreported amine catalyst 11 was employed in entry 7 (Table 2); see Supporting Information.
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    • 19F NMR yield); however facile postreaction racemization is observed.
    • 19F NMR yield); however facile postreaction racemization is observed.
  • 47
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    • 2 and MeOH to afford β-trifluoromethyl alcohols in high yield and enantioselectivity.
    • 2 and MeOH to afford β-trifluoromethyl alcohols in high yield and enantioselectivity.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.