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Volumn 51, Issue 6, 2010, Pages 942-945

1,4-syn-Asymmetric induction in the titanium-mediated aldol reactions of chiral methyl α-silyloxy ketones

Author keywords

Acetate aldol reactions; Chiral ketones; Stereoselective reactions; Titanium enolates

Indexed keywords

ALDEHYDE DERIVATIVE; KETONE DERIVATIVE; SILANE; TITANIUM;

EID: 73249118765     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.12.046     Document Type: Article
Times cited : (14)

References (36)
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    • Helmchen G., Hoffmann R.W., Mulzer J., and Schaumann E. (Eds), Georg Thieme, Stuttgart
    • Braun M. In: Helmchen G., Hoffmann R.W., Mulzer J., and Schaumann E. (Eds). Houben-Weyl. Methods of Organic Chemistry. Stereoselective Synthesis Vol. E21b (1995), Georg Thieme, Stuttgart 1603-1666
    • (1995) Houben-Weyl. Methods of Organic Chemistry. Stereoselective Synthesis , vol.E21b , pp. 1603-1666
    • Braun, M.1
  • 6
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    • Mahrwald R. (Ed), Wiley-VCH, Weinheim
    • In: Mahrwald R. (Ed). Modern Aldol Reactions (2004), Wiley-VCH, Weinheim
    • (2004) Modern Aldol Reactions
  • 10
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    • note
    • The term acetate aldol reaction refers to any aldol transformation involving unsubstituted enolates, which encompasses the reactions from acetate esters or methyl ketones.
  • 12
    • 0028853930 scopus 로고
    • In contrast to other aldol reactions that proceed through closed transition states, both chair- and boat-like transition state models have been invoked to rationalize the stereochemical outcome of such reactions. For theoretical calculations on boron-mediated aldol reactions of ethyl and methyl ketones, see:
    • In contrast to other aldol reactions that proceed through closed transition states, both chair- and boat-like transition state models have been invoked to rationalize the stereochemical outcome of such reactions. For theoretical calculations on boron-mediated aldol reactions of ethyl and methyl ketones, see:. Bernardi A., Gennari C., Goodman J.M., and Paterson I. Tetrahedron: Asymmetry 6 (1995) 2613-2636
    • (1995) Tetrahedron: Asymmetry , vol.6 , pp. 2613-2636
    • Bernardi, A.1    Gennari, C.2    Goodman, J.M.3    Paterson, I.4
  • 13
    • 39349099300 scopus 로고    scopus 로고
    • For an insightful analysis of some key structural elements that control the stereochemical outcome of boron-mediated acetate aldol reactions, see:
    • For an insightful analysis of some key structural elements that control the stereochemical outcome of boron-mediated acetate aldol reactions, see:. Paton R.S., and Goodman J.M. J. Org. Chem. 73 (2008) 1253-1263
    • (2008) J. Org. Chem. , vol.73 , pp. 1253-1263
    • Paton, R.S.1    Goodman, J.M.2
  • 14
    • 34548633472 scopus 로고    scopus 로고
    • For recent examples illustrating the complexity of acetate aldol reactions, see:
    • For recent examples illustrating the complexity of acetate aldol reactions, see:. Paterson I., Findlay A.D., and Anderson E.A. Angew. Chem., Int. Ed. 46 (2007) 6699-6702
    • (2007) Angew. Chem., Int. Ed. , vol.46 , pp. 6699-6702
    • Paterson, I.1    Findlay, A.D.2    Anderson, E.A.3
  • 16
    • 0000444632 scopus 로고
    • For studies on stereoselective aldol reactions from chiral α-hydroxy methyl ketones, see:
    • For studies on stereoselective aldol reactions from chiral α-hydroxy methyl ketones, see:. Trost B.M., and Urabe H. J. Org. Chem. 55 (1990) 3982-3983
    • (1990) J. Org. Chem. , vol.55 , pp. 3982-3983
    • Trost, B.M.1    Urabe, H.2
  • 28
    • 73249135788 scopus 로고    scopus 로고
    • note
    • The Mukaiyama aldol reaction of the leucine-derived methyl α-OTES ketone with isobutyraldehyde affords the corresponding syn aldol as a single diastereomer (dr syn/anti 98:2) but in low yield (36%).
  • 34
    • 73249125143 scopus 로고    scopus 로고
    • note
    • The aldol reaction was also carried out at -94 °C. However, it turned out to be too sluggish and required longer reaction times.
  • 35
    • 73249152745 scopus 로고    scopus 로고
    • note
    • 4) and concentrated. The resulting oil was analyzed by NMR and purified by flash chromatography (hexanes/EtOAc).
  • 36
    • 0001353039 scopus 로고
    • At this point, it is worth mentioning that the boron-mediated aldol reactions from mandelic-derived tert-butyldimethylsilyloxy methyl ketone provided a roughly equimolar mixture of two diastereomeric aldol adducts, which was assumed to be due to the competition between two boat-like transition states, see: Therefore, it is clear the crucial role of the metal on the transition states and the stereochemical outcome of such reactions
    • At this point, it is worth mentioning that the boron-mediated aldol reactions from mandelic-derived tert-butyldimethylsilyloxy methyl ketone provided a roughly equimolar mixture of two diastereomeric aldol adducts, which was assumed to be due to the competition between two boat-like transition states, see:. Masamune S., Sato T., Kim B., and Wollmann T.A. J. Am. Chem. Soc. 108 (1986) 8279-8281 Therefore, it is clear the crucial role of the metal on the transition states and the stereochemical outcome of such reactions
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 8279-8281
    • Masamune, S.1    Sato, T.2    Kim, B.3    Wollmann, T.A.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.