Rao Weidong, Boyle Joshua William, Chan Philip Wai Hong
Jiangsu Key Laboratory of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, P. R. China.
School of Chemistry, Monash University, Clayton, Victoria, 3800, Australia.
Chemistry. 2016 May 4;22(19):6532-6. doi: 10.1002/chem.201600915. Epub 2016 Mar 24.
A synthetic method that relies on a gold(I)-catalyzed cycloisomerization of 1-en-3,9-diyne esters to spiro[4.4]non-2-ene-substituted 1,2-dihydronaphthalenes is described. Robust with a wide variety of substitution patterns tolerated, the reaction provides the first example of a one-step strategy to construct such novel and architecturally challenging members of the carbocycle family in good to excellent yields. A mechanism is proposed in which the sequential cycloisomerization pathway was thought to involve a gold-catalyzed 1,3-acyloxy migration/Nazarov cyclization followed by a formal [4+2] cycloaddition to give the tetracarbocyclic product.
描述了一种合成方法，该方法依赖于金（I）催化的1-烯-3,9-二炔酯环异构化反应生成螺[4.4]壬-2-烯取代的1,2-二氢萘。该反应对多种取代模式具有耐受性，稳健性强，是构建碳环家族中此类新颖且结构具有挑战性的成员的一步策略的首个实例，产率良好至优异。提出了一种机理，其中连续的环异构化途径被认为涉及金催化的1,3-酰氧基迁移/纳扎罗夫环化反应，随后进行形式上的[4+2]环加成反应以生成四环产物。
