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Volumn 72, Issue 2, 2007, Pages 435-441

Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions: Allylation or 2-propynylation and aldol reaction

Author keywords

[No Author keywords available]

Indexed keywords

ALDOL REACTIONS; HYDROXY GROUP; HYDROXYACETONES;

EID: 33846217034     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0618573     Document Type: Article
Times cited : (7)

References (43)
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    • (2000) Stimulating Concepts in Chemistry , pp. 39-64
    • Tietze, L.F.1    Haunert, F.2
  • 2
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    • See also:, and
    • See also: Pellissier, H. Tetrahedron 2006, 62, 1619-1665 and 2143-2173.
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    • See also: Ishikawa. T.; Miyahara, T.; Asakura, M.; Higuchi, S.; Miyauchi, Y.; Saito, S. Org. Lett. 2005, 7, 1211-121. We succeeded in achieving domino processes leading to benzofurans from cyclohexane-1,3-diones in one pot in which 13 elementary processes were operating.
    • See also: Ishikawa. T.; Miyahara, T.; Asakura, M.; Higuchi, S.; Miyauchi, Y.; Saito, S. Org. Lett. 2005, 7, 1211-121. We succeeded in achieving domino processes leading to benzofurans from cyclohexane-1,3-diones in one pot in which 13 elementary processes were operating.
  • 5
    • 33846223219 scopus 로고    scopus 로고
    • Since domino reactions are defined as processes of making two or more bonds in which the subsequent reactions take place at the functionalities obtained in the former step, the processes presented in this work are not necessarily the domino processes. For the definition of the domino processes, see ref 1
    • Since domino reactions are defined as processes of making two or more bonds in which the subsequent reactions take place at the functionalities obtained in the former step, the processes presented in this work are not necessarily the domino processes. For the definition of the domino processes, see ref 1.
  • 6
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    • For review, see:, Trost, B. M, Fleming, I, Eds, Pergamon: Oxford, Chapter 2.3
    • For review, see: Jones, A. B. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, Chapter 2.3.
    • (1991) Comprehensive Organic Synthesis , vol.7
    • Jones, A.B.1
  • 15
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    • For reviews, see: g, Trost, B. M, Fleming, I, Eds, Pergamon: Oxford, Chapter 2.4
    • For reviews, see: (g) Hassner, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 1, Chapter 2.4.
    • (1991) Comprehensive Organic Synthesis , vol.1
    • Hassner, A.1
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    • (b) McElvain, Org. React. 1948, 4, 256-268.
    • (1948) Org. React , vol.4 , pp. 256-268
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    • (d) Finley, K. T. Chem. Rev. 1964, 64, 573-589.
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  • 25
    • 0000166356 scopus 로고    scopus 로고
    • It was reported that when LDA was employed for generating chiral enolates from N-(benzyloxyacetyl)- or N-(tert- butyldimethylsilyloxyacetyl)-oxazolidinone followed by addition of neryl bromide, no alkylation proceeded at all for the TBDMS-protection case and only 20% yield of alkylated product was obtained for the benzyl-protection case. However, when other chiral auxiliary such as (-)-ephedrine-derived imidazolidinone was employed, its N-(benzyloxyacetyl) derivative led to 49% yield of alkylated product (LDA, neryl bromide), see: Cardillo, G.; Orena, M.; Romero, M.; Sandri, S. Tetrahedron 1989, 45, 1501-1508.
    • It was reported that when LDA was employed for generating chiral enolates from N-(benzyloxyacetyl)- or N-(tert- butyldimethylsilyloxyacetyl)-oxazolidinone followed by addition of neryl bromide, no alkylation proceeded at all for the TBDMS-protection case and only 20% yield of alkylated product was obtained for the benzyl-protection case. However, when other chiral auxiliary such as (-)-ephedrine-derived imidazolidinone was employed, its N-(benzyloxyacetyl) derivative led to 49% yield of alkylated product (LDA, neryl bromide), see: Cardillo, G.; Orena, M.; Romero, M.; Sandri, S. Tetrahedron 1989, 45, 1501-1508.
  • 26
    • 33846219083 scopus 로고    scopus 로고
    • As indicated in ref 8, Evans substrate such as N-(tert- butyldimethylsilyloxyacetyl)oxazolidinone did not lead to any alkylation product at all (LDA, neryl bromide, THF). Our observation for 1c similar to that previous case may be ascribed to the same cause, which is not completely clear at present. We must await future systematic studies for elucidating the exact nature of the hydroxyacetone enolates concerned.
    • As indicated in ref 8, Evans substrate such as N-(tert- butyldimethylsilyloxyacetyl)oxazolidinone did not lead to any alkylation product at all (LDA, neryl bromide, THF). Our observation for 1c similar to that previous case may be ascribed to the same cause, which is not completely clear at present. We must await future systematic studies for elucidating the exact nature of the hydroxyacetone enolates concerned.
  • 28
    • 33846226015 scopus 로고    scopus 로고
    • 2, 0 °C) to give bis-[(2S,3S)-3-tert- butyldiphenylsiloxy-4,4-dimethyl]oxolan-2-yl ether. We are now trying to convert this dimer (hemiacetal anhydride) to 23.
    • 2, 0 °C) to give bis-[(2S,3S)-3-tert- butyldiphenylsiloxy-4,4-dimethyl]oxolan-2-yl ether. We are now trying to convert this dimer (hemiacetal anhydride) to 23.
  • 35
    • 33846230523 scopus 로고    scopus 로고
    • 2 (AB quartet) for X, which tentatively led us to conclude that X contains polyalkylated products such as 34, 35, or 36, though a final decision must await further reliable structural analyses. On the basis of these considerations, the yield of the polyalkylated products was calculated to be 2.5%.
    • 2 (AB quartet) for X, which tentatively led us to conclude that X contains polyalkylated products such as 34, 35, or 36, though a final decision must await further reliable structural analyses. On the basis of these considerations, the yield of the polyalkylated products was calculated to be 2.5%.
  • 36
    • 33846214355 scopus 로고    scopus 로고
    • Because of the higher volatility of 30, significant loss of products during evaporative workup was unavoidable. Accordingly, the yield indicated in the text was determined by NMR for a sample containing EtOAc stemmed from column chromatographic separation.
    • Because of the higher volatility of 30, significant loss of products during evaporative workup was unavoidable. Accordingly, the yield indicated in the text was determined by NMR for a sample containing EtOAc stemmed from column chromatographic separation.
  • 37
    • 33846264042 scopus 로고    scopus 로고
    • Structures of difficult to separate polyalkylation products (three components) were estimated to be 37 (two diastereoisomers) and 38 on the basis of NMR analysis of the mixture. Chemical yield was calculated based on these structures.
    • Structures of difficult to separate polyalkylation products (three components) were estimated to be 37 (two diastereoisomers) and 38 on the basis of NMR analysis of the mixture. Chemical yield was calculated based on these structures.
  • 38
    • 33846234262 scopus 로고
    • For a review on alkylations of heteroatom-stabilized carbanions other than acyloins, see:, Trost, B. M, Fleming, I, Eds, Pergamon: Oxford, Chapter 1.4
    • For a review on alkylations of heteroatom-stabilized carbanions other than acyloins, see: Cheshire, D. R. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 1.4.
    • (1991) Comprehensive Organic Synthesis , vol.3
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  • 39
    • 0001010896 scopus 로고    scopus 로고
    • In this series of outstanding comprehensive surveys, no description of the alkylation or allylation of acyloins is presented, see also: Evans, D. A.; Sacks, C. E.; Kleschick, W. A.; Taber, T. R. J. Am. Chem. Soc. 1979, 101, 6789-6791 in which regioselective alkylation of 2-butanone-based 3-PhS-substituted N,N-dimethylhydrazone under thermodynamically controlled conditions [KH, tert-BuOK (0.03 equiv). THF, reflux, then iodoalkane, 0 °C to rt) is described.
    • In this series of outstanding comprehensive surveys, no description of the alkylation or allylation of acyloins is presented, see also: Evans, D. A.; Sacks, C. E.; Kleschick, W. A.; Taber, T. R. J. Am. Chem. Soc. 1979, 101, 6789-6791 in which regioselective alkylation of 2-butanone-based 3-PhS-substituted N,N-dimethylhydrazone under thermodynamically controlled conditions [KH, tert-BuOK (0.03 equiv). THF, reflux, then iodoalkane, 0 °C to rt) is described.
  • 40
    • 0001081787 scopus 로고    scopus 로고
    • The acyloin framework is a key structural unit of many natural products, and chiral α-hydroxy ketones (acyloins) are versatile synthetic intermediates for diversified bioactive compounds, see: (a) Bel-Rhlid, R.; Fauve, A.; Veschambre, H. J. Org. Chem. 1989, 54, 3221-3223.
    • The acyloin framework is a key structural unit of many natural products, and chiral α-hydroxy ketones (acyloins) are versatile synthetic intermediates for diversified bioactive compounds, see: (a) Bel-Rhlid, R.; Fauve, A.; Veschambre, H. J. Org. Chem. 1989, 54, 3221-3223.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.