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Volumn 43, Issue 26, 2002, Pages 4661-4665

Highly enantioselective catalytic Michael reaction of α-substituted malonates using La-linked-BINOL complex in the presence of HFIP (1,1,1,3,3,3-hexafluoroisopropanol)

Author keywords

substituted malonates; Additive effects of HFIP (1,1,1,3,3,3 hexafluoroisopropanol); Catalytic asymmetric Michael reaction; La linked BINOL complex

Indexed keywords

1,1,1,3,3,3 HEXAFLUOROISOPROPANOL; ALCOHOL DERIVATIVE; MALONIC ACID DERIVATIVE; PROPANOL; UNCLASSIFIED DRUG;

EID: 0037189163     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(02)00882-1     Document Type: Article
Times cited : (61)

References (35)
  • 13
    • 0009546761 scopus 로고    scopus 로고
    • 3 solution was used.
  • 14
    • 0009515333 scopus 로고    scopus 로고
    • Both enantiomers of the La-linked-BINOL complex are now commercially available from STREM Chemicals, Inc., 7 Mulliken Way, Dexter Industrial Park, Newburyport, MA 01950-4098, USA (Fax: +(1)-978-465-3104). When they were used for the catalytic asymmetric Michael reaction of 9 to 7 (10 mol% of the catalyst was used in the reported conditions in Ref. 3b), the Michael adduct 12 was obtained in 57% yield and 94% ee.
  • 15
    • 0009537490 scopus 로고    scopus 로고
    • The catalytic asymmetric Michael reaction of more reactive α-substituted β-keto esters and α-substituted α-cyano esters to very reactive enones were reported by us and others. See Ref. 2.
  • 16
    • 0009546762 scopus 로고    scopus 로고
    • Only reactive electrophiles, such as allyl bromide (80%), reacted with 5 to give a reasonable yield, while other electrophiles, such as 5-bromo-1-pentene (30%), ethyl 4-bromobutanoate (15%), 4-bromo-1-butene (0%), and methyl acrylate (0%), gave highly unsatisfactory results.
  • 17
    • 0009515674 scopus 로고    scopus 로고
    • Lower chemical yields were obtained in other concentrations (57% in 0.2 M and 80% in 2.0 M), although the enantiomeric excesses were unchanged in both cases (99% ee).
  • 18
    • 0009514037 scopus 로고    scopus 로고
    • The absolute configurations of 3a, 3c, and 3f were already determined by transformation of the known compound 4 to 3 via 5 and 6; see Ref. 8. The absolute configurations of 3b, 3d, 3e, and 3g were tentatively determined on the basis of the absolute configuration of 3a and previous results. See Ref. 3.
  • 31
    • 0009537492 scopus 로고    scopus 로고
    • Lower chemical yields were obtained in other concentrations (73% in 0.2 M and 93% in 2.0 M), although the enantiomeric excesses were unchanged in both cases (99% ee).
  • 32
    • 0009481862 scopus 로고    scopus 로고
    • note
  • 33
    • 0009506875 scopus 로고    scopus 로고
    • Using the best conditions, Michael reaction of 2a to 2-cyclohexene-1-one (7) gave the corresponding (S)-Michael adduct in 63% yield and 94% ee, while the reaction to 2-cycloheptene-1-one (8) gave only trace amount of the corresponding Michael adduct.
  • 34
    • 0009506876 scopus 로고    scopus 로고
    • a 18.0 in DMSO).
  • 35
    • 0009546862 scopus 로고    scopus 로고
    • In contrast, the addition of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether did not accelerate the reaction.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.