메뉴 건너뛰기




Volumn 46, Issue 11, 2007, Pages 1893-1896

Reactions of iminium ions with Michael acceptors through a Morita-Baylis-Hillman-type reaction: Enantiocontrol and applications in synthesis

Author keywords

C C coupling; Lewis acids; Lewis bases; Mannich reaction; Morita Baylis Hillman reaction

Indexed keywords

MOLECULAR DYNAMICS; REACTION KINETICS; SYNTHESIS (CHEMICAL);

EID: 34249688755     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200604715     Document Type: Article
Times cited : (85)

References (64)
  • 10
    • 34250868112 scopus 로고
    • U.S. Patent 3,074,999
    • a) M. Rauhut, H. Currier, U.S. Patent 3,074,999, 1963;
    • (1963)
    • Rauhut, M.1    Currier, H.2
  • 13
    • 0037139579 scopus 로고    scopus 로고
    • for an example of a vinylogous MBH reaction, see: d S. A. Frank, D. J. Mergott, W. R. Roush, J. Am. Chem. Soc. 2002, 124, 2404;
    • for an example of a vinylogous MBH reaction, see: d) S. A. Frank, D. J. Mergott, W. R. Roush, J. Am. Chem. Soc. 2002, 124, 2404;
  • 29
    • 0022517466 scopus 로고    scopus 로고
    • An intramolecular variant has been described involving a pendent enone; see: a K. H. Melching, H. Hiemstra, W. J. Klaver, W. N. Speckamp, Tetrahedron Lett. 1986, 27, 4799;
    • An intramolecular variant has been described involving a pendent enone; see: a) K. H. Melching, H. Hiemstra, W. J. Klaver, W. N. Speckamp, Tetrahedron Lett. 1986, 27, 4799;
  • 31
    • 33744826542 scopus 로고    scopus 로고
    • The reaction could also be classed as a vinylogous Mannich reaction. An asymmetric Mannich reaction has been described for the synthesis of β-amino acid derivatives; see
    • The reaction could also be classed as a vinylogous Mannich reaction. An asymmetric Mannich reaction has been described for the synthesis of β-amino acid derivatives; see: Y. Chi, S. H. Gellman, J. Am. Chem. Soc. 2006, 128, 6804;
    • (2006) J. Am. Chem. Soc , vol.128 , pp. 6804
    • Chi, Y.1    Gellman, S.H.2
  • 32
    • 4043089374 scopus 로고    scopus 로고
    • for a review of β-amino acids in biology, see
    • for a review of β-amino acids in biology, see: G. Lelais, D. Seebach, Biopolymers 2004, 76, 206.
    • (2004) Biopolymers , vol.76 , pp. 206
    • Lelais, G.1    Seebach, D.2
  • 33
    • 0037064515 scopus 로고    scopus 로고
    • Such conditions had previously been employed for MBH reactions (usually in stoichiometric amounts) with aldehydes. See: a) L. M. Walsh, C. L. Winn, J. M. Goodman, Tetrahedron Lett. 2002, 43, 8219;
    • Such conditions had previously been employed for MBH reactions (usually in stoichiometric amounts) with aldehydes. See: a) L. M. Walsh, C. L. Winn, J. M. Goodman, Tetrahedron Lett. 2002, 43, 8219;
  • 37
    • 34250791896 scopus 로고    scopus 로고
    • for other terminal electrophiles in this context, see Refs. [7e-i]; for a review, see: T. Kataoka, H. Kinoshita, Eur. J. Org. Chem. 2005, 45.
    • for other terminal electrophiles in this context, see Refs. [7e-i]; for a review, see: T. Kataoka, H. Kinoshita, Eur. J. Org. Chem. 2005, 45.
  • 38
    • 84982066078 scopus 로고    scopus 로고
    • It has been reported that similar adducts derived from alkyl iminium ions are stable; see: H. Boehme, M. Haake, Chem. Ber. 1972, 105, 2233
    • It has been reported that similar adducts derived from alkyl iminium ions are stable; see: H. Boehme, M. Haake, Chem. Ber. 1972, 105, 2233.
  • 40
    • 24644434994 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2005, 44, 5468.
    • (2005) Chem. Int. Ed , vol.44 , pp. 5468
    • Angew1
  • 41
    • 46549103031 scopus 로고
    • For a discussion of this issue, see the following reviews: a
    • For a discussion of this issue, see the following reviews: a) W. N. Speckamp, H. Hiemstra, Tetrahedron 1985, 41, 4367;
    • (1985) Tetrahedron , vol.41 , pp. 4367
    • Speckamp, W.N.1    Hiemstra, H.2
  • 43
    • 34250842935 scopus 로고    scopus 로고
    • When the reaction was carried out at -78°C (2 equiv of TiCl 4 and MVK, and subsequent treatment with DBU, the MBH adduct was not produced and the starting material, N,O-acetal 1, along with the hydroxy aminal derivative were recovered. This result is intriguing since Goodman and co-workers have demonstrated that the generation of the required β-chloro titanium enolate is facile at this temperature see Ref, 10a, It is possible that at -78°C, N,O-acetal 1 is converted into its kinetically stable α-chloro derivative, which only becomes unstable with respect to an iminium ion at higher temperatures, namely -20°C. When the reaction was carried out at -20°C, the MBH adduct was isolated in 67% yield. Attempts to expand the scope of the alkene beyond MVK were unsuccessful
    • 4 and MVK, and subsequent treatment with DBU), the MBH adduct was not produced and the starting material, N,O-acetal 1, along with the hydroxy aminal derivative were recovered. This result is intriguing since Goodman and co-workers have demonstrated that the generation of the required β-chloro titanium enolate is facile at this temperature (see Ref. [10a]). It is possible that at -78°C, N,O-acetal 1 is converted into its kinetically stable α-chloro derivative, which only becomes unstable with respect to an iminium ion at higher temperatures, namely -20°C. When the reaction was carried out at -20°C, the MBH adduct was isolated in 67% yield. Attempts to expand the scope of the alkene beyond MVK were unsuccessful.
  • 44
    • 34250889687 scopus 로고    scopus 로고
    • This combination gave similar results as produced with TiCl4 alone
    • 4 alone.
  • 45
    • 34250817816 scopus 로고    scopus 로고
    • 2Al-I, which is suitably active to allow generation of the β-iodo enolate of methyl acrylate (see Ref. [10d]), did not lead to the required adduct 2g; the delivery of the ethyl rather than the enolate ligand to the iminium ion was the only process observed.
    • 2Al-I, which is suitably active to allow generation of the β-iodo enolate of methyl acrylate (see Ref. [10d]), did not lead to the required adduct 2g; the delivery of the ethyl rather than the enolate ligand to the iminium ion was the only process observed.
  • 46
    • 0001375989 scopus 로고    scopus 로고
    • For the procedure for preparation of (S)-ethyl 2-propenethiolate, see: G. Braude, J. Org. Chem. 1957, 22, 1675.
    • For the procedure for preparation of (S)-ethyl 2-propenethiolate, see: G. Braude, J. Org. Chem. 1957, 22, 1675.
  • 47
    • 0021028138 scopus 로고
    • For previous syntheses of, -heliotridine, see: a
    • For previous syntheses of (+)-heliotridine, see: a) A. R. Chamberlin, J. Y. L. Chung, J. Am. Chem. Soc. 1983, 105, 3653;
    • (1983) J. Am. Chem. Soc , vol.105 , pp. 3653
    • Chamberlin, A.R.1    Chung, J.Y.L.2
  • 54
    • 33750254071 scopus 로고    scopus 로고
    • 2OTf, which is a more powerful Lewis acid than its components: E. L. Myers, C. P. Butts, V. K. Aggarwal, Chem. Commun. 2006, 4434.
    • 2OTf, which is a more powerful Lewis acid than its components: E. L. Myers, C. P. Butts, V. K. Aggarwal, Chem. Commun. 2006, 4434.
  • 55
    • 3943048796 scopus 로고    scopus 로고
    • This transformation is commonly observed when metathesis is difficult. For a review, see: B. Schmidt, Eur. J. Org. Chem. 2004, 1865
    • This transformation is commonly observed when metathesis is difficult. For a review, see: B. Schmidt, Eur. J. Org. Chem. 2004, 1865.
  • 57
  • 60
  • 62
    • 33750488744 scopus 로고    scopus 로고
    • V. K. Aggarwal, G. Y. Fang, C. G. Kokotos, J. Richardson, M. G. Unthank, Tetrahedron 2006, 62, 11 297. Alkylation of 8 occurs exclusively at the lone pair of electrons trans to the camphor moiety.
    • e) V. K. Aggarwal, G. Y. Fang, C. G. Kokotos, J. Richardson, M. G. Unthank, Tetrahedron 2006, 62, 11 297. Alkylation of 8 occurs exclusively at the lone pair of electrons trans to the camphor moiety.
  • 63
    • 34250801861 scopus 로고    scopus 로고
    • See the Supporting Information for 1H NMR spectra of the low-temperature experiments
    • 1H NMR spectra of the low-temperature experiments.
  • 64
    • 34250861023 scopus 로고    scopus 로고
    • eq to temperature suggests an entropy (TΔS) and enthalpy (ΔH) term which are of a similar order of magnitude.
    • eq to temperature suggests an entropy (TΔS) and enthalpy (ΔH) term which are of a similar order of magnitude.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.