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Volumn 49, Issue 39, 2010, Pages 7068-7071

Enantiodifferentiating endo-selective oxylactonization of ortho-alk-l-enylbenzoate with a lactate-derived aryl-λ3-iodane

Author keywords

Asymmetric synthesis; Hypervalent compounds iodine; Lactones; Oxidation

Indexed keywords

ASYMMETRIC SYNTHESIS; ENANTIO-DIFFERENTIATING; ENANTIOSELECTIVE; HYPERVALENT COMPOUNDS; HYPERVALENT IODINE; LACTONES; OPTICALLY ACTIVE;

EID: 77956935988     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201003503     Document Type: Article
Times cited : (183)

References (75)
  • 1
    • 0013167416 scopus 로고    scopus 로고
    • (Ed. T. Wirth) Springer Berlin
    • a) Hypervalent Iodine Chemistry (Ed.: T. Wirth), Springer, Berlin, 2003
    • (2003) Hypervalent Iodine Chemistry
  • 59
    • 77956928706 scopus 로고    scopus 로고
    • Exo selectivity has been observed for iodolactonization of 7a[15b] and for oxylactonization of ortho-alk-1-enylbenzoic acid.[15c]
    • a) Exo selectivity has been observed for iodolactonization of 7a[15b] and for oxylactonization of ortho-alk-1-enylbenzoic acid.[15c]
  • 65
    • 77956899603 scopus 로고    scopus 로고
    • The regio- and diastereoselective oxidative cyclization of alkenes using an achiral λ3-iodane has recently attracted much attention, see
    • The regio- and diastereoselective oxidative cyclization of alkenes using an achiral λ3-iodane has recently attracted much attention, see
  • 69
    • 77956925041 scopus 로고    scopus 로고
    • N2 must give the R isomer. For the acetoxylactonization, a 1, 3-dioxolan-2-yl cation may serve as an intermediate in the double inversion. Results for the enantioselectivity of the minor γ lactone product are rationalized by a combination of these reaction pathways.
    • The absolute stereochemistry of the γ-lactone products 9 a and 11 a depended on the reaction conditions. There are some conceivable reaction pathways for the formation of the minor γ lactone: 1) The internal carboxylic acid participates toward the benzylic position of the intermediate A. In this case, the (S)- isomer of the γ lactone must form in the reactions with 1-6, judging from the preferential formation of the (S)-isomer of the δlactone. 2) Dioxytosylation of the vinyl group, followed by internal nucleophilic substitution at the benzylic position. The SN1 route must give a racemic product, and the SN2 must give the R isomer. For the acetoxylactonization, a 1, 3-dioxolan-2-yl cation may serve as an intermediate in the double inversion. Results for the enantioselectivity of the minor γ lactone product are rationalized by a combination of these reaction pathways.
  • 71
    • 77956933473 scopus 로고    scopus 로고
    • Experimental evidence for secondary I-O interactions in solution was obtained in a complex of PhI+OH and 18-crown-6 by cold-spray ionization mass spectroscopy.[19b] Intramolecular interaction has been discussed in the solid state.[4b, c, 10d, e]
    • a) Experimental evidence for secondary I-O interactions in solution was obtained in a complex of PhI+OH and 18-crown-6 by cold-spray ionization mass spectroscopy.[19b] Intramolecular interaction has been discussed in the solid state.[4b, c, 10d, e]
  • 75
    • 77956938517 scopus 로고    scopus 로고
    • n (n = 0-2). Thus, the oxygen atom bound at the ortho position of the aryliodane has little interfering effect on the solvent coordination to the iodonium ion.
    • Electrospray ionization mass spectrometry of 1-(diacetoxyiodo)- 2-methoxy benzene showed a similar result to that of 1-(diac- etoxyiodo)-2, 4, 6-trimethylbenzene in the relative intensities of M+-(MeCN)n (n = 0-2). Thus, the oxygen atom bound at the ortho position of the aryliodane has little interfering effect on the solvent coordination to the iodonium ion.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.