Experiment and Theory of Bimetallic Pd-Catalyzed α-Arylation and Annulation for Naphthalene Synthesis
Experiment and Theory of Bimetallic Pd-Catalyzed α-Arylation and Annulation for Naphthalene Synthesis
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DOI：
10.1021/acscatal.1c02731
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发表时间：
2021-08-05
期刊：
影响因子：
12.9
通讯作者：
Michaelis, David J.
中科院分区：
文献类型：
--
作者：
Ence, Chloe C.;Martinez, Erin E.;Michaelis, David J.
本文报道了双齿2-膦基咪唑配体与Pd（I）和Pd（II）配合物的合成及其催化合成取代萘的活性。该方法包括通过顺序的酮α-芳基化偶联芳基碘和2当量的酮，然后以区域选择性方式环化以产生二取代和四取代的萘。优秀的底物范围为芳基碘和酮的合作伙伴证明，包括杂芳基碘。双金属Pd络合物在该转化中比单金属Pd催化剂反应性高得多。密度泛函理论计算、同位素效应实验和底物竞争实验用于研究双金属机制、反应性和选择性。
We report the synthesis of bimetallic Pd(I) and Pd(II) complexes with bidentate 2-phosphinoimidazole ligands and their catalytic activity to generate substituted naphthalenes. This process involves the coupling of an aryl iodide and 2 equiv of a ketone via sequential ketone alpha-arylation and then annulation to generate disubstituted and tetrasubstituted naphthalenes in a regioselective manner. Excellent substrate scope for both aryl iodide and ketone partners is demonstrated, including that for heteroaryl iodides. Bimetallic Pd complexes are much more reactive than monometallic Pd catalysts in this transformation. Density functional theory calculations, isotope effect experiments, and substrate competition experiments were used to examine bimetallic mechanisms, reactivity, and selectivity.