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Volumn 137, Issue 22, 2015, Pages 7091-7094

Chiral Brønsted Acid as a True Catalyst: Asymmetric Mukaiyama Aldol and Hosomi-Sakurai Allylation Reactions

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; CONDENSATION REACTIONS; ENANTIOSELECTIVITY; KETONES;

EID: 84935891610     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b04168     Document Type: Article
Times cited : (55)

References (55)
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    • TMS silyl enol ether of acetophenone is 103 times less reactive than TMS silyl ketene acetal of methyl isobutylate, see
    • TMS silyl enol ether of acetophenone is 103 times less reactive than TMS silyl ketene acetal of methyl isobutylate, see: Mayr, H.; Kempf, B.; Ofial, A. R. Acc. Chem. Res. 2003, 36, 66
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    • For reviews on chiral phosphoric acid catalysis, see
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    • note
    • For 29Si and 31P NMR spectra, see the Supporting Information.
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    • note
    • TMS-A1 and TMS- C1 may exist in equilibrium with their isomers (P- N -SiMe3, P-Se/ O -SiMe3, and S- O -SiMe3).
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    • In situ generation of silyl Lewis acids by the reaction of chiral phosphoric acids with silyl compounds, see: Rowland, E. B.; Rowland, G. B.; Rivera-Otero, E.; Antilla, J. C. J. Am. Chem. Soc. 2007, 129, 12084
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    • note
    • The reason for such a reactivity difference of the catalysts remains unclear, and computational studies to rationalize this result are underway.
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    • For the beneficial effect of bulky para substituents at the 3,3′-aryl groups on enantioselectivity in chiral phosphoric acid catalysis, see
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    • note
    • It is reported that the substituent on the sulfonyl group of the phosphoramide catalyst has a significant influence on the yield but not on the enantioselectivity; see: ref 10f and references therein.
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    • For usage of this base to differentiate the reaction pathway between Lewis acid and Bronsted acid catalysis, see
    • For usage of this base to differentiate the reaction pathway between Lewis acid and Bronsted acid catalysis, see: Mathieu, B.; Ghosez, L. Tetrahedron 2002, 58, 8219
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    • note
    • This result implies that our new catalyst has the potential to enable the asymmetric anti -selective Mukaiyama aldol reaction.
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    • note
    • Treatment of a 1.5:1 mixture of E-and Z-1b with 5 mol % of catalyst B4 at -100 C for 1 h resulted in a 1:7.7 mixture of E-and Z-1b, see the Supporting Information.
  • 47
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    • For examples of Brønsted acid-catalyzed isomerization of silyl enol ethers, see
    • For examples of Brønsted acid-catalyzed isomerization of silyl enol ethers, see: Deyine, A.; Dujardin, G.; Mammeri, M.; Poirier, J.-M. Synth. Commun. 1998, 28, 1817
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    • For reviews on catalytic asymmetric allylation of carbonyl compounds with allylsilanes, see: In; Wiley-VCH: Weinheim, Germany, Chapter 10.
    • For reviews on catalytic asymmetric allylation of carbonyl compounds with allylsilanes, see: Denmark, S. E.; Almstead, N. G. In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH: Weinheim, Germany, 2000; Chapter 10.
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    • note
    • Unsubstituted or γ-substituted allylsilanes did not react even at room temperature.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.