Oxidative Annulation of Acetanilides with Alkynes Catalyzed by Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides
Oxidative Annulation of Acetanilides with Alkynes Catalyzed by Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides
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DOI：
10.1002/ajoc.201900139
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发表时间：
2019-04
影响因子：
2.7
通讯作者：
Ryo Yoshimura;Y. Shibata;Soichi Yoshizaki;Jyunichi Terasawa;Takayuki Yamada;Ken Tanaka
中科院分区：
文献类型：
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作者：
Ryo Yoshimura;Y. Shibata;Soichi Yoshizaki;Jyunichi Terasawa;Takayuki Yamada;Ken Tanaka
研究表明，一种含N-苯基氨基甲酰基侧基的阳离子双（Cp）铑（III）配合物（CpA 1 RhIII）对乙酰苯胺与内炔的氧化[3+2]成环反应具有很高的催化活性。CpA 1 RhIII配合物在对称内炔（二苯基乙炔和6-十二炔）反应中的催化活性高于Cp*-铑（III）配合物，并且与具有两个乙氧基羰基的Cp-铑（III）配合物（CpERhIII）相当。另一方面，CpA 1 RhIII复合物在不对称内炔（1-苯基-1-丙炔和1-苯基-1-己炔）的反应中表现出明显高于CpERhIII复合物的催化活性.此外，CpA 1 RhIII复合物在具有两个不对称缺电子内炔（2-丁炔酸乙酯）的乙酰苯胺的氧化串联[2+2+2]环化-内酰胺化中的催化活性也与CpERhIII复合物相当。
It has been established that a cationic cyclopentadienyl (Cp) rhodium(III) complex with a pendantN‐phenylcarbamoyl moiety (CpA1RhIII) showed high catalytic activity towards the oxidative [3+2] annulation of acetanilides with internal alkynes to produce substituted indoles. Catalytic activity of the CpA1RhIIIcomplex in the reactions of symmetric internal alkynes (diphenylacetylene and 6‐dodecyne) was higher than that of the Cp*‐rhodium(III) complex and comparable to that of a Cp‐rhodium(III) complex with two ethoxycarbonyl groups (CpERhIII). On the other hand, the CpA1RhIIIcomplex showed significantly higher catalytic activity than the CpERhIIIcomplex in the reactions of unsymmetric internal alkynes (1‐phenyl‐1‐propyne and 1‐phenyl‐1‐hexyne). Additionally, the catalytic activity of the CpA1RhIIIcomplex in the oxidative tandem [2+2+2] annulation‐lactamization of acetanilides with two unsymmetric electron‐deficient internal alkynes (ethtyl 2‐butynoate) was also comparable to that of the CpERhIIIcomplex.