doi:10.1016/j.tetlet.2005.02.124
Copyright © 2005 Elsevier Ltd All rights reserved.
A synthetic approach to the plakoridines modeled on a biogenetic theory
Laura L. Etchellsa, Ali Sardarian†, a and Roger C. Whitehead
, a, 
aThe School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK
Received 10 February 2005;
revised 22 February 2005;
accepted 23 February 2005.
Available online 10 March 2005.
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Abstract
An expedient synthetic route to the fully substituted pyrrolidine ring system of the plakoridines is described using an approach modeled on a plausible biosynthetic pathway.
Keywords: Biomimetic; Cascade; Natural product; Fatty acid
Scheme 3. Reagents and conditions: (i) C15H31COCl, SnCl4, CH2Cl2, −5 °C, 1 h, 98%; (ii) H2NNH2, NaOH, HOCH2CH2OH, Δ, 72 h, 60%; (iii) TMSCHN2, CH3OH, toluene, rt, 1 h, 72% or CH3OH, Amberlite® IR 120 (H), Δ, 72 h, 69%.
Scheme 4. Reagents and conditions: (i) Br2, CH3OH, Na2CO3, rt, 2 h, 84%; (ii) 0.005 M H2SO4, H2O, dioxane, rt, 1.5 h; (iii) KHMDS, THF, −78 °C to rt, 79%; (iv) mCPBA, CH2Cl2, −10 °C to rt, 2 h then work-up with NaHCO3(aq), 56%; (v) NaHCO3, H2O, dioxane, rt, 74% from 18; (vi) Br2, acetone, H2O, −20 °C to 10 °C, 6 h, 56% (75% based on recovered 6).
Scheme 5. Reagents and conditions: (i) H2O, rt, 3 h, 97%; (ii) CDCl3, rt, 12 d, 38% for 24, 4% for 25, 15% for 26.
Scheme 6. Reagents and conditions: (i) CDCl3, rt, 10 d, 39%.