Wang Jingjing, Ting Samuel Z Y, Harvey Joanne E
Centre for Biodiscovery, School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6140, New Zealand.
Beilstein J Org Chem. 2015 Oct 5;11:1815-22. doi: 10.3762/bjoc.11.197. eCollection 2015.
Bestmann ylide [(triphenylphosphoranylidene)ketene] acts as a chemical linchpin that links nucleophilic entities, such as alcohols or amines, with carbonyl moieties to produce unsaturated esters and amides, respectively. In this work, the formation of α,β,γ,δ-unsaturated esters (dienoates) is achieved through the coupling of Bestmann ylide, an alcohol and an α,β-unsaturated aldehyde. Primary and secondary alcohols, including allylic alcohols, are suitable substrates; the newly formed alkene has an E-geometry. Strategically, this represents a highly efficient route to unsaturated polyketide derivatives. A linchpin approach to the synthesis of a major fragment of the natural products zampanolide and dactylolide is investigated using Bestmann ylide to link the C16-C20 alcohol with the C3-C8 aldehyde fragment.
贝斯德曼叶立德（三苯基磷亚基烯酮）充当一种化学关键中间体，它将亲核实体（如醇或胺）与羰基部分相连，分别生成不饱和酯和酰胺。在这项工作中，α,β,γ,δ-不饱和酯（二烯酸酯）的形成是通过贝斯德曼叶立德、一种醇和一种α,β-不饱和醛的偶联实现的。伯醇和仲醇，包括烯丙醇，都是合适的底物；新形成的烯烃具有E-构型。从策略上讲，这是一条通往不饱和聚酮衍生物的高效路线。研究了一种利用贝斯德曼叶立德将C16 - C20醇与C3 - C8醛片段相连来合成天然产物赞帕诺内酯和指状内酯主要片段的关键中间体方法。
