Recent Progress on Arylation with Aryne through Three-Component Reaction

Abstract

The three component reaction has the advantages of simple operation and efficient reaction, in line with the principles of atomic economy and green environmental protection. At present, the arylation without transition metal catalyst is mainly divided into three types of as following: (1) the direct arylation, (2) the insertion of aryne into σ-bond or π-bond, and (3) the three-component reactions involving aryne. Compared with the direct arylation and the insertion of aryne into σ-bond or π-bond, the mechanism of three component reactions involving aryne is still unclear, and the published reviews are still lacking. In order to facilitate the scientific researchers to consult and understand the three-component reaction involved in aryne, the progresses in the three-component reaction involving aryne in recent years are reviewed. Keywords aryne; three component reaction; carbon and heteroatom; arylation 芳炔作为一类重要的反应活性中间体一直备受人 们的关注, 其参与的反应为构建碳-碳键和碳-杂键提供 了新的反应模式 [1][2][3][4][5][6] , 并且在天然产物、生物碱和药物中 间体的合成中具有广泛的应用 [7] . 自 1983 年 Kobayashi 课题组 [8] 首次报道 2-(三甲基甲硅烷基)苯基三氟甲磺酸 酯为苯炔前体, 在氟负离子作用下高效生成苯炔的方法 以来(Scheme 1), 芳炔参与的芳基化反应推动了芳炔化 学的快速发展.

Macrocyclization of carbon dioxide with 3-triflyloxybenzynes and tetrahydrofuran: straightforward access to 14-membered macrolactones

“…Since the group of Kobayashi in 1983 developed a facile method for the generation of benzynes from ortho -silyl aryl triflates, 8 the use of these highly reactive species in organic synthesis has been extensively investigated for the assembly of various polysubstituted arenes and benzo-fused cyclic compounds. 9 Notably, several multicomponent reactions involving benzynes have also been developed for the transformation of CO 2 by Yoshida, 10 Biju, 11 Kobayashi 12 and our group. 13 In the aspect of the synthesis of benzo-fused heterocycles, for example, the group of Yoshida in 2006 first reported a three-component cyclization between arynes, imines and CO 2 for the synthesis of valuable benzoxazinone derivatives (Scheme 1a).…”