Synthesis of migrastatin-core analogues.

<p>Reagents and conditions: (a) 5-hexenoic acid, Ph ₃P, DIAD, PhCH₃, rt, 3h, 69%; (b) Grubbs 2^nd, PhCH₃, reflux, 25 min, 68%; (c) HF. Py, THF, rt, 18h, 61%; (d) CBr₄, Ph ₃P polymer-bound, CH₂Cl_2, rt, 50 min; (e) <b>12</b>, DBU, PhCH₃ then <b>11</b>, rt, 1.5h; (f) Na/Hg, MeOH, rt, 3h, 51% over three steps; (g) Grubbs 2^nd, PhCH₃, reflux, 15 min, 99%; (h) HF. Py, THF, rt, 38h, 84%; (i) Lawesson reagent, CH₂Cl₂, mw, 100 °C, 10 min; (j) <b>9</b>, Ph ₃P, DIAD, PhCH₃, rt, 15h, 42%; (k) Grubbs 2^nd, PhCH₃, reflux, 15 min, 88%; (l) HF. Py, THF, rt, 18h, 85%; (m) TMSCl, LHMDS, THF, 0 °C, 2h; (n) Pd(OAc)₂, CH₃CN, rt, 3h, 64% over two steps; (o) HF. Py, THF, rt, 18h, 90%.