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Volumn 47, Issue 27, 2008, Pages 5060-5062

Stereoselective dearomatizing addition of nucleophiles to uncomplexed benzene rings: A route to carbocyclic sugar analogues

Author keywords

Carbohydrates; Dearomatization; Diastereoselectivity; Oxazolines; Pseudosugars

Indexed keywords

BENZENE; CHEMICAL REACTIONS; LITHIUM; SUGAR (SUCROSE);

EID: 49849100686     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200801078     Document Type: Article
Times cited : (29)

References (46)
  • 22
    • 53549088224 scopus 로고    scopus 로고
    • Dearomatized products of addition to phenyl rings have been observed previously only in less than 10% yield: Prof. A. I. Meyers, personal communication, 2004.
    • Dearomatized products of addition to phenyl rings have been observed previously only in less than 10% yield: Prof. A. I. Meyers, personal communication, 2004.
  • 23
    • 9744245274 scopus 로고    scopus 로고
    • Oxazolines 1 and 16 were synthesized by a previously reported method: S. Crosignani, A. C. Young, B. Linclau, Tetrahedron Lett. 2004, 45, 9611.
    • Oxazolines 1 and 16 were synthesized by a previously reported method: S. Crosignani, A. C. Young, B. Linclau, Tetrahedron Lett. 2004, 45, 9611.
  • 25
    • 0041409652 scopus 로고    scopus 로고
    • DMPU and hexamethylphosphoramide (HMPA) have been shown to promote other reactions involving dearomatizing addition steps, probably by facilitating the formation of ion pairs; see: J. Clayden, F. E. Knowles, C. J. Menet, Synlett 2003, 1701;
    • DMPU and hexamethylphosphoramide (HMPA) have been shown to promote other reactions involving dearomatizing addition steps, probably by facilitating the formation of ion pairs; see: J. Clayden, F. E. Knowles, C. J. Menet, Synlett 2003, 1701;
  • 27
    • 0029827163 scopus 로고    scopus 로고
    • [3] but none performed as well as 1.
    • [3] but none performed as well as 1.
  • 28
    • 53549088492 scopus 로고    scopus 로고
    • CCDC 670194 (3), CCDC 670195 (11), CCDC 670196 (12), CCDC 670197 (18a), and CCDC 670198 (18c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • CCDC 670194 (3), CCDC 670195 (11), CCDC 670196 (12), CCDC 670197 (18a), and CCDC 670198 (18c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 29
    • 53549123732 scopus 로고    scopus 로고
    • The stereoselectivity of both the dearomatizing addition and the alkylation appears to be greater than 10:1, as no stereoisomeric dearomatized products were observable in the NMR spectrum of the crude reaction mixture. We assume that the configuration of the product arises from coordination of isopropyllithium to the basic nitrogen atom of the oxazoline, followed by 1,4-addition to the 2-position of the p-methoxyphenyl ring from the face anti to the 4-phenyl substituent of the oxazoline ring. Details of the mechanism are still under investigation; however, preliminary attempted trapping experiments suggest that radical intermediates are not involved
    • The stereoselectivity of both the dearomatizing addition and the alkylation appears to be greater than 10:1, as no stereoisomeric dearomatized products were observable in the NMR spectrum of the crude reaction mixture. We assume that the configuration of the product arises from coordination of isopropyllithium to the basic nitrogen atom of the oxazoline, followed by 1,4-addition to the 2-position of the p-methoxyphenyl ring from the face anti to the 4-phenyl substituent of the oxazoline ring. Details of the mechanism are still under investigation; however, preliminary attempted trapping experiments suggest that radical intermediates are not involved.
  • 30
    • 0000204167 scopus 로고    scopus 로고
    • B. A. Barner, A. I. Meyers, J. Am. Chem. Soc. 1984, 106, 1865. The oxazolidine intermediates 5 and 9 were formed as single stereoisomers, the configuration of which was not assigned.
    • B. A. Barner, A. I. Meyers, J. Am. Chem. Soc. 1984, 106, 1865. The oxazolidine intermediates 5 and 9 were formed as single stereoisomers, the configuration of which was not assigned.
  • 39
    • 0033097654 scopus 로고    scopus 로고
    • A number of known carbasugar analogues contain quaternary centers and/or alkyl branches
    • A number of known carbasugar analogues contain quaternary centers and/or alkyl branches: A. Berecibar, C. Grandjean, A. Siriwardena, Chem. Rev. 1999, 99, 779;
    • (1999) Chem. Rev , vol.99 , pp. 779
    • Berecibar, A.1    Grandjean, C.2    Siriwardena, A.3
  • 45
    • 53549093475 scopus 로고    scopus 로고
    • 1H NMR spectrum.
    • 1H NMR spectrum.
  • 46
    • 53549086052 scopus 로고    scopus 로고
    • The configuration of the adducts was assigned by analogy with 3, 18a, and 18c.
    • The configuration of the adducts was assigned by analogy with 3, 18a, and 18c.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.