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Volumn 351, Issue 16, 2009, Pages 2567-2572

Highly efficient synthesis of quaternary α-hydroxy phosphonates via lewis acid-catalyzed hydrophosphonylation of ketones

Author keywords

Asymmetric synthesis; Functionalized ketones; Hydrophosphonylation; Ketones; Titanium

Indexed keywords


EID: 70549103416     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200900531     Document Type: Article
Times cited : (61)

References (68)
  • 14
    • 33947092127 scopus 로고
    • Abramov-type and silylphosphonylation reactions of limited simple ketones using high toxic trialkyl phosphite and expensive trimethylsilyl dialkyl phosphite were also efficient. However, formation of at least 1 equivalent of by-product accompanied the synthesis of the quaternary a-hydroxy phosphonate; a) D. A. Evans, K. M. Hurst, J. M. Takacs, J. Am. Chem. Soc. 1978, 100, 3467;
    • (1978) J. Am. Chem. Soc. , vol.100 , pp. 3467
    • Evans, D.A.1    Hurst, K.M.2    Takacs, J.M.3
  • 34
    • 67749124294 scopus 로고    scopus 로고
    • i) D. Uraguchi, T. Ito, T. Ooi, J. Am. Chem. Soc. 2009, 131, 3836. For the chiral diol-titanium-catalyzed asymmetric hydrophosphonylation of aldehydes, see:
    • (2009) J. Am. Chem. Soc. , vol.131 , pp. 3836
    • Uraguchi, D.1    Ito, T.2    Ooi, T.3
  • 42
    • 70549083159 scopus 로고    scopus 로고
    • [7e]
    • [7e]
  • 58
    • 70549096498 scopus 로고    scopus 로고
    • note
    • a) It was suspected that the great difference on the reactivity of the reaction for different Lewis acids was mostly dependent on the possible phosphonate-phosphite equilibrium; The Lewis acid activates both the dimethyl phosphite and ketone, while the activation of dimethyl phosphite is more important for the hydrophosphonylation of ketone in this paper. Although the precise order of different Lewis acids for the activation of dimethyl phosphite was hard to determine owing to the difficult observation of the metallo-phosphite, it was believed that basic counterions and a suitable acidity of the Lewis acid were beneficical for the activation of dimethyl phosphite,
  • 59
    • 70549100521 scopus 로고    scopus 로고
    • Elevating the reaction temperature was beneficial for the hydrophosphonylation of ketone
    • b) Elevating the reaction temperature was beneficial for the hydrophosphonylation of ketone,
  • 60
    • 70549092382 scopus 로고    scopus 로고
    • 4
    • 4.
  • 61
    • 70549092381 scopus 로고    scopus 로고
    • 4 as the catalyst. The yields had no obvious improvement using other Lewis acids under neat conditions
    • 4 as the catalyst. The yields had no obvious improvement using other Lewis acids under neat conditions.
  • 62
    • 70549096497 scopus 로고    scopus 로고
    • Using 4-methoxybenzoic acid as the additive, the enantioselectivity of the reaction could be further increased to 65% ee albeit with a reduced reactivity
    • e) Using 4-methoxybenzoic acid as the additive, the enantioselectivity of the reaction could be further increased to 65% ee albeit with a reduced reactivity.
  • 64
    • 70549110525 scopus 로고    scopus 로고
    • See Experimental Section
    • b) See Experimental Section.
  • 65
    • 70549086209 scopus 로고    scopus 로고
    • Half of the products were unknown previously, and only six products were reported to be prepared via hydrophosphonylation of ketones with moderate to good yields. The quaternary α-hydroxy phosphonates are easily hydrolyzed to the corresponding phosphonic acids, see
    • a) Half of the products were unknown previously, and only six products were reported to be prepared via hydrophosphonylation of ketones with moderate to good yields. The quaternary α-hydroxy phosphonates are easily hydrolyzed to the corresponding phosphonic acids, see:


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.