Room Temperature Decarboxylative and Oxidative [2+2+2] Annulation of Benzoic Acids with Alkynes Catalyzed by an Electron-Deficient Rhodium(III) Complex
Room Temperature Decarboxylative and Oxidative [2+2+2] Annulation of Benzoic Acids with Alkynes Catalyzed by an Electron-Deficient Rhodium(III) Complex
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DOI：
10.1002/chem.201703928
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发表时间：
2018-01-09
影响因子：
4.3
通讯作者：
Tanaka, Ken
中科院分区：
文献类型：
--
作者：
Honjo, Yusaku;Shibata, Yu;Tanaka, Ken
研究了缺电子型（5）-Rh（Ⅲ）[（CpRhIII）-Rh-E]配合物在室温下催化苯甲酸与炔的脱羧和氧化[2+2+2]成环反应生成取代萘的反应。添加剂和溶剂的适当选择对于这种转变至关重要。该催化剂体系允许使用氧作为末端氧化剂，并拓宽了底物范围，包括芳香族和脂肪族炔。在该催化中，（CpRhIII）-Rh-E催化剂的缺电子性质将引起强铑相互作用，这加速了脱羧以及C-H键断裂。
It has been established that an electron-deficient ((5)-cyclopentadienyl)rhodium(III) [(CpRhIII)-Rh-E] complex is capable of catalyzing the decarboxylative and oxidative [2+2+2] annulation of benzoic acids with alkynes to produce substituted naphthalenes at room temperature. The appropriate choice of the additive and the solvent is crucial for this transformation. This catalyst system allowed use of oxygen as a terminal oxidant and broadened the substrate scope including both aromatic and aliphatic alkynes. In this catalysis, the electron deficient nature of the (CpRhIII)-Rh-E catalyst would cause the strong rhodium- interaction, which accelerates the decarboxylation as well as the C-H bond cleavage.