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Volumn 10, Issue 21, 2004, Pages 5386-5397

Asymmetric desymmetrization based on an intramolecular haloetherification: A highly effective and recyclable chiral nonracemic auxiliary, 2-exo-methyl-3-endo-phenyl-5-norbornene-2-carboxaldehyde, for meso-1,3- and meso-1,4-diols

Author keywords

Asymmetric synthesis; Chiral auxiliaries; Desymmetrization; Diols; Norbornene

Indexed keywords

ALCOHOLS; ALDEHYDES; CRYSTALLIZATION; ETHERS; HYDROLYSIS;

EID: 8344270145     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400444     Document Type: Article
Times cited : (13)

References (37)
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    • For example, see: a) A. P. Davis, Angew. Chem. 1997, 109, 609-612; Angew. Chem. Int. Ed. Engl. 1997, 36, 591-594;
    • (1997) Angew. Chem. , vol.109 , pp. 609-612
    • Davis, A.P.1
  • 2
    • 0030933630 scopus 로고    scopus 로고
    • For example, see: a) A. P. Davis, Angew. Chem. 1997, 109, 609-612; Angew. Chem. Int. Ed. Engl. 1997, 36, 591-594;
    • (1997) Angew. Chem. Int. Ed. Engl. , vol.36 , pp. 591-594
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    • d) F. Theil, Chem. Rev. 1995, 95, 2203-2227;
    • (1995) Chem. Rev. , vol.95 , pp. 2203-2227
    • Theil, F.1
  • 9
    • 1642438321 scopus 로고    scopus 로고
    • For recent studies on desymmetrization of meso-1,2-diols, see: a) S. Mizuta, M. Sadamori, T. Fujimoto, I. Yamamoto, Angew. Chem. 2003, 115, 3505-3507; Angew. Chem. Int. Ed. 2003, 42, 3383-3385;
    • (2003) Angew. Chem. , vol.115 , pp. 3505-3507
    • Mizuta, S.1    Sadamori, M.2    Fujimoto, T.3    Yamamoto, I.4
  • 10
    • 0042029706 scopus 로고    scopus 로고
    • For recent studies on desymmetrization of meso-1,2-diols, see: a) S. Mizuta, M. Sadamori, T. Fujimoto, I. Yamamoto, Angew. Chem. 2003, 115, 3505-3507; Angew. Chem. Int. Ed. 2003, 42, 3383-3385;
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 3383-3385
  • 28
    • 8344234257 scopus 로고    scopus 로고
    • note
    • At the beginning of the work, we supposed that discrimination between the two oxygen atoms depends on the stability of the cationic intermediates from intramolecular bromoetherification. (See ref. [5], where the direction of discrimination expected from the activation energy is the same as the direction from the stability of the cationic intermediates.) Later, during the work on optical resolution (ref. [6]), the obtained direction was found to be opposite to the direction expected from the stability of the cation intermediates, but the same as the order of activation energies. We therefore suppose that the genuine factor for discrimination of the two oxygen atoms of the acetal is the difference in the activation energies of the transition states.
  • 31
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    • Chiral hydrobenzoin is readily available in both enantiomeric forms by asymmetric synthesis. See: Z.-M. Wang, K. B. Sharpless, J. Org. Chem. 1994, 59, 8302-8303.
    • (1994) J. Org. Chem. , vol.59 , pp. 8302-8303
    • Wang, Z.-M.1    Sharpless, K.B.2
  • 32
    • 8344249531 scopus 로고    scopus 로고
    • note
    • CCDC-230171 contains the supplementary crystallo-graphic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/ retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK: fax: (+44)1223-336-033; or e-mail; deposit@ccdc.cam.ac. uk).
  • 35
    • 8344290511 scopus 로고    scopus 로고
    • note
    • Compound 7a is stable when it stands at room temperature although it has an aldehyde functionionality. Its stability may depend on its crystallization at room temperature, although other norbornene aldehydes, such as 1a, 1b, and 7b, are oils and need refrigeration for prolonged storage.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.