Research Institute for Interdisciplinary Science, Okayama University , 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.
J Org Chem. 2017 Jun 16;82(12):6242-6258. doi: 10.1021/acs.joc.7b00848. Epub 2017 Jun 5.
A palladium-catalyzed benzannulation with o-bromobenzyl alcohols enabled the facile construction of phenanthrene skeletons via the sequential multiple carbon-carbon bond formations. A variety of multisubstituted phenanthrenes were synthesized by the reaction of (Z)-β-halostyrenes with o-bromobenzyl alcohols as well as by the three-component coupling of alkynes, aryl bromides, and o-bromobenzyl alcohols. The electron-deficient phosphine ligand played an important role to control the sequential oxidative addition of two different organic halides employed, which realized the selective formation of the desired phenanthrenes in good yields. This synthetic protocol was also applicable to the synthesis of the highly fused polycyclic aromatic hydrocarbons such as tetraphenes.
钯催化的邻溴苄醇苯并环化反应能够通过连续的多碳-碳键形成来轻松构建菲骨架。通过（Z）-β-卤代苯乙烯与邻溴苄醇的反应以及炔烃、芳基溴化物和邻溴苄醇的三组分偶联反应，可以合成各种多取代的菲。缺电子膦配体对于控制所使用的两种不同有机卤化物的顺序氧化加成起着重要作用，这实现了所需菲的选择性形成，产率良好。该合成方案也适用于高度稠合的多环芳烃如四苯的合成。
