메뉴 건너뛰기




Volumn 43, Issue 25, 2004, Pages 3307-3310

Construction of C-S bonds with a quaternary stereocenter through a formal Michael reaction: Asymmetric synthesis of tertiary thiols

Author keywords

Asymmetric synthesis; Chirality; Lewis acids; Michael addition; Thiols

Indexed keywords

ALCOHOLS; OXIDATION; STEREOCHEMISTRY; SUBSTITUTION REACTIONS; SULFUR;

EID: 4544227437     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200453889     Document Type: Article
Times cited : (39)

References (50)
  • 1
    • 0035925367 scopus 로고    scopus 로고
    • and previous review articles in the series
    • For an updated account on the synthesis of thiols, sulfides, and derivatives, see: D. J. Procter, J. Chem. Soc. Perkin Trans. 1 2001, 335-354 and previous review articles in the series.
    • (2001) J. Chem. Soc. Perkin Trans. 1 , pp. 335-354
    • Procter, D.J.1
  • 2
    • 0034251445 scopus 로고    scopus 로고
    • For a review on metal-catalyzed C-S bond formation, see: T. Kondo, T. Mitsudo, Chem. Rev. 2000, 100, 3205-3220.
    • (2000) Chem. Rev. , vol.100 , pp. 3205-3220
    • Kondo, T.1    Mitsudo, T.2
  • 15
    • 0037126839 scopus 로고    scopus 로고
    • f) P. McDaid, Y. Chen, L. Deng, Angew. Chem. 2002, 114, 348-350; Angew. Chem. Int. Ed. 2002, 41, 338-340;
    • (2002) Angew. Chem. Int. Ed. , vol.41 , pp. 338-340
  • 20
    • 0009276253 scopus 로고
    • For the synthesis of quaternary C-S systems other than thiols asymmetrically, see: Sulfoxides: a) D. A. Evans, G. C. Andews, Acc. Chem. Res. 1974, 7, 147-155;
    • (1974) Acc. Chem. Res. , vol.7 , pp. 147-155
    • Evans, D.A.1    Andews, G.C.2
  • 24
    • 4544298094 scopus 로고    scopus 로고
    • note
    • The preparation of a tertiary arylsulfide is described in reference [5a] (53% yield and 85% ee); another one in reference [5b] (43% yield and 10% ee).
  • 25
    • 33750456293 scopus 로고
    • (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford
    • M. E. Jung in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, p. 17.
    • (1991) Comprehensive Organic Synthesis , vol.4 , pp. 17
    • Jung, M.E.1
  • 28
    • 0001521888 scopus 로고
    • Reviews: a) K. Fuji, Chem. Rev. 1993, 93, 2037-2066;
    • (1993) Chem. Rev. , vol.93 , pp. 2037-2066
    • Fuji, K.1
  • 30
    • 0032473509 scopus 로고    scopus 로고
    • b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401;
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 388-401
  • 31
    • 0001227615 scopus 로고    scopus 로고
    • c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597;
    • (2001) Angew. Chem. , vol.113 , pp. 4725-4732
    • Christoffers, J.1    Mann, A.2
  • 32
    • 0035905575 scopus 로고    scopus 로고
    • c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597;
    • (2001) Angew. Chem. Int. Ed. , vol.40 , pp. 4591-4597
  • 34
    • 0142194987 scopus 로고    scopus 로고
    • The use of Michael addition reactions in the construction of quaternary stereocenters: J. Christoffers, A. Baro, Angew. Chem. 2003, 115, 1726-1728; Angew. Chem. Int. Ed. 2003, 42, 1688-1690.
    • (2003) Angew. Chem. , vol.115 , pp. 1726-1728
    • Christoffers, J.1    Baro, A.2
  • 35
    • 0037541354 scopus 로고    scopus 로고
    • The use of Michael addition reactions in the construction of quaternary stereocenters: J. Christoffers, A. Baro, Angew. Chem. 2003, 115, 1726-1728; Angew. Chem. Int. Ed. 2003, 42, 1688-1690.
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 1688-1690
  • 38
    • 0038034781 scopus 로고    scopus 로고
    • For further development by others, see: T. Kataoka, H. Kinoshita, S. Kinoshita, T. Osamura, S. Watanabe, T. Iwamura, O. Muraoka, G. Tanabe, Angew. Chem. 2003, 115, 2995-2997; Angew. Chem. Int. Ed. 2003, 42, 2889-2891.
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 2889-2891
  • 39
    • 0022413342 scopus 로고
    • For Lewis acid-assisted cyclization of N-enoyl thioureas leading to 1,3-thiazines, see: M. Dzurilla, P. Kutschy, P. Kristan, Synthesis 1985, 933-934.
    • (1985) Synthesis , pp. 933-934
    • Dzurilla, M.1    Kutschy, P.2    Kristan, P.3
  • 40
    • 4544278076 scopus 로고    scopus 로고
    • note
    • 3 led to variable quantities of undesired side products.
  • 41
    • 4544357711 scopus 로고    scopus 로고
    • CCDC-228804 contains the supplementary crystallographic 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 CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
  • 42
    • 4544320956 scopus 로고    scopus 로고
    • note
    • Mixtures of different E/Z composition were obtained by either column chromatography- or recrystallization-driven enrichment of the original E/Z mixture. See Supporting Information for details.
  • 43
    • 0035891621 scopus 로고    scopus 로고
    • For example, it has been described recently that the conjugate addition of lithium thiophenolate to an E and Z mixture of a cyclic enone gives exclusively one diastereomeric addition product. T. J. Houghton, C. Soongyu, V. H. Rawal, Org. Lett. 2001, 3, 3615-3617.
    • (2001) Org. Lett. , vol.3 , pp. 3615-3617
    • Houghton, T.J.1    Soongyu, C.2    Rawal, V.H.3
  • 44
    • 4544334342 scopus 로고    scopus 로고
    • note
    • Note for this case it is the opposite configuration of both the auxiliary and the resulting tertiary sulfanyl. Also, see reference [25].
  • 45
    • 0037696083 scopus 로고    scopus 로고
    • and references therein
    • The synthesis of β,β-disubstituted Michael acceptors with either solely E or solely Z configuration is, in general, not so straightforward. For further information, see, for instance, N. Zhu, D. G. Hall, J. Org. Chem. 2003, 68, 6066-6069, and references therein.
    • (2003) J. Org. Chem. , vol.68 , pp. 6066-6069
    • Zhu, N.1    Hall, D.G.2
  • 46
    • 4544294566 scopus 로고    scopus 로고
    • note
    • There are two possible rationales: kinetic production of the observed diastereomer through any reaction pathway involving a common intermediate reachable from both E- and Z-configured enoyl derivatives, and thermodynamic equilibration of the formed diastereomeric products before final hydrolysis. Among the possible pathways for the first rationale would be the virtual E/Z isomerization of the substrate under the reaction conditions. After analysis by NMR spectroscopy of aliquots taken for a set of reactions at times corresponding to different degrees of reaction conversion, however, no detectable E/Z isomerization could be observed, and this possibility can be ruled out.
  • 50
    • 4544284407 scopus 로고    scopus 로고
    • note
    • The enantiomer of 10 is obtained in >97% ee from the reduction of 7 under otherwise identical conditions.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.