ja401717b_si_001.pdf (1.8 MB)
Asymmetric Total Synthesis of (−)-Amphidinolide V through Effective Combinations of Catalytic Transformations
journal contribution
posted on 2016-02-19, 12:22 authored by Ivan Volchkov, Daesung LeeAn
asymmetric total synthesis of (−)-amphidinolide V was
accomplished. The synthesis features a base-catalyzed alkynyl silane
alcoholysis/ring-closing enyne metathesis sequence for facile construction
of a 1,3-diene motif. A diene RCM followed by a ring-contractive allylic
transposition of cyclic silyl ethers was incorporated for the stereoselective
installation of a functionalized 1,5-diene subunit. An efficient proline-mediated
direct cross-aldol condensation of two advanced aldehyde intermediates
was utilized for the construction of a key α,β-unsaturated
epoxyaldehyde. This total synthesis demonstrates the prowess of metal-catalyzed
transformations in complex molecule synthesis.