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. 2000 Apr 1;41(14):2319-2322.
doi: 10.1016/S0040-4039(00)00158-1. Epub 2002 Aug 2.

An enantioselective synthesis of the C2-C16 segment of antitumor macrolide laulimalide1

Arun K Ghosh  1 , Yong Wang  1
Affiliations

An enantioselective synthesis of the C2-C16 segment of antitumor macrolide laulimalide1

Arun K Ghosh et al. Tetrahedron Lett. .

Abstract

An enantioselective synthesis of the C2-C16 segment of the novel antitumor agent laulimalide is described. The key steps involve a highly diastereoselective allylation, ring-closing olefin metathesis of a homoallylic alcohol derived acrylate ester, a stereoselective anomeric alkylation and an elaboration of an exo-methylene unit by a Julia olefination reaction.

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Figures

Figure. 1.
Figure. 1.
Retrosynthetic Analysis.
Scheme 1.
Scheme 1.
(a) MsCl, Et3N, CH2Cl2, 0°C; (b) NaCN, DMSO, 60°C (95%); (c) DIBAL-H, CH2Cl2, 0°C (93%); (d) CH2=CHCH2B[(−)-Ipc]2, THF, −100°C (75%); (e) CH2=CHCOCl, Et3N, 0 to 23°C, CH2Cl2 (76%); (f) Cl2(PCy3)2Ru=CHPh (10 mol%), Ti(OiPr)4 (30 mol%), CH2Cl2, 40°C (72%); (g) DIBAL-H, CH2Cl2, −78°C then Ac2O, pyridine, DMAP, −78 to 23°C; (h) BF3·OEt2, CH2Cl2, CH2=CHCH2SiMe3, −78°C (82%); (i) Li, NH3, (78%); (j) I2, PPh3, imidazole, MeCN–Et2O (97%)
Scheme 2.
Scheme 2.
(a) NaH, PhSO2CH2CO2Me, EtOH (83%); (b) NaH, DMF, iodide 11, 60°C (91%); (c) LiBH4, THF, 0 to 23°C; (d) PhCOCl, Et3N, DMAP (cat), CH2Cl2; (e) Mg, HgCl2 (cat), EtOH (44%)
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References

    1. This work has been presented at the 218th American Chemical Society National Meeting, New Orleans, August 22–26, 1999; contribution number: Medn 234.
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