| 内容提要: |
An 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 ringcontractive allylic transposition of cyclic silyl ethers was incorporated for the stereoselective installation of a functionalized 1,5-diene subunit. An efficient prolinemediated 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. |