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. 1997 Apr 7;38(14):2427-2430.
doi: 10.1016/S0040-4039(97)00416-4. Epub 2000 Mar 17.

SYNTHETIC STUDIES OF ANTITUMOR MACROLIDE LAULIMALIDE: ENANTIOSELECTIVE SYNTHESIS OF THE C3-C14 SEGMENT BY A CATALYTIC HETERO DIELS-ALDER STRATEGY

Arun K Ghosh  1 , Packiarajan Mathivanan  1 , John Cappiello  1
Affiliations

SYNTHETIC STUDIES OF ANTITUMOR MACROLIDE LAULIMALIDE: ENANTIOSELECTIVE SYNTHESIS OF THE C3-C14 SEGMENT BY A CATALYTIC HETERO DIELS-ALDER STRATEGY

Arun K Ghosh et al. Tetrahedron Lett. .

Abstract

The C3-C14 segment of the novel antitumor agent laulimalide has been constructed enantioselectively by utilizing a catalytic asymmetric hetero Diels-Alder reaction of benzyloxyacetaldehyde and Danishefsky's diene followed by Ferrier rearrangement and asymmetric conjugate reaction as the key steps.

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Figures

Scheme 1:
Scheme 1:
(a) K-10, OTBS, CH2Cl2, 0°C, 2 h; (b) NaBH4, MeOH, 0°C, 30 min; (c) MOMCl, iPr2NEt, CH2Cl2, 23°C, 8 h; (d) liq. NH3, −78°C, 1 h; (e) MCl, Et3N, DMAP, CH2Cl2, 0°C, 30 min; (f)n-Et4N+CN-, CH3CN-PhH (1:1), reflux,4 h; (g) Diba1-H, Et2O, −78°C, 4h; (h) NaH, THF, 0°C, (EtO)2P(O)CH2CO2Et, 1 h;(i) 1 M LiOH, 23°C, 6 h; (j) Me3CCOC1, Et3N, THF, 0°C then N-lithiosultam, −78°C, 2 h; (k) Me2CuLi, Et2O, −78°C, 8 h; (m) 1M LiOH, 23°C, 5 h; (n) MeLi, THF, 0°C then TMSC1.
See this image and copyright information in PMC

References

    1. Quinoa E; Kskou Y; Crews P J Org. Chem. 1988,53,3642;
    2. Corley DG; Herb R; Moore RE; Scheuer PJ; paul VJ J. Org. Chem. 1988,53, 3644.
    1. Jefford CW;Bernrdinelli G; Tanaka J-I; Higa T Tetrahedron Lett. 1996,37, 159;
    2. Tanaka J-I; Higa T;Bernrdinell Gi,.;Jefford CW Chemistry Lett. 1996,255.
    1. Corey EJ; Imai, Zhang H-Y J. Am. Chem. soc 1991, 113, 728;
    2. Corey E Isihara K Tetrahedron Lett. 1992, 33, 6807;
    3. Evans DA; Miller SJ; Lectka T J. Am. Chem. soc. 1993, 115, 6460;
    4. Evans DA; Murry JA; Mat PV; Norcross RD; Miller SJ Angew. Chem. Int. Ed. Engl 1995, 34, 798;
    5. Ghosh AK; Mathivanan P; Cappiello J Tetrahedron Lett. 1996, 37, 3815; - PMC - PubMed
    6. Davies IW; Senanayake CH; Larsen RD; Verhoeven TR; Reider PJ Tetrahedron Lett. 1996, 37, 1725;
    7. Evans DA; Barnes DM Tetrahedron Lett. 1997, 38, 57;
    8. Pfaltz A Acta Chimica Scandinavia 1996, 50, 189 and references cited therein.
    1. Ghosh AK; Mathivanan P; Cappiello J; Krishnan K Tetrahedron: Asymmetry 1996, 7, 2615 For other recent catalytic reports, see ref. 5. - PMC - PubMed
    1. Terada M; Mikami K; Nakai T Tetrahedron Lett. 1991, 32, 935;
    2. Corey EJ; Cywin CL; Roper TD Tetrahedron Lett. 1992, 33, 6907;
    3. Gao Q; Maruyama T; Mouri M; Yamamoto H J. org. Chem 1992, 57, 1957;
    4. Mikmli, Motoyama Y; Terada M J. Am. Chem. soc., 1994, 116, 2811;
    5. Motoyama Y; Mikami KJ Chem. soc. Chem. Commun 1994, 1563;
    6. Keck G Li X-Y; Krishnamurthy D J. org. Chem 1995, 60, 5998.

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