Department of Chemistry, Norwegian University of Science and Technology, Høgskoleringen 5, 7491, Trondheim, Norway.
ChemistryOpen. 2022 May;11(5):e202200030. doi: 10.1002/open.202200030. Epub 2022 Mar 10.
Gold-catalyzed transformations of 1,3-diarylpropargyl alcohols and various aryl nucleophiles were studied. Selective tunable synthetic methods were developed for 1,1,3-triarylallenes, diaryl-indenes and tetraaryl-allyl target products by C3 nucleophilic substitution and subsequent intra- or intermolecular hydroarylation, respectively. The reactions were scoped with regards to gold(I)/(III) catalysts, solvent, temperature, and electronic and steric effects of both the diarylpropargyl alcohol and the aryl nucleophiles. High yields of triaryl-allenes and diaryl-indenes by gold(III) catalysis were observed. Depending on the choice of aryl nucleophile and control of reaction temperature, different product ratios have been obtained. Alternatively, tetraaryl-allyl target products were formed by a sequential one-pot tandem process from appropriate propargyl substrates and two different aryl nucleophiles. Corresponding halo-arylation products (I and Br; up to 95 % 2-halo-diaryl-indenes) were obtained in a one-pot manner in the presence of the respective N-halosuccinimides (NIS, NBS).
研究了金催化的 1,3-二芳基炔丙醇和各种芳基亲核试剂的转化。通过 C3 亲核取代和随后的分子内或分子间氢芳基化，分别为 1,1,3-三芳基丙二烯、二芳基茚和四芳基烯丙基目标产物开发了选择性可调的合成方法。考察了金（I）/（III）催化剂、溶剂、温度以及芳基炔丙醇和芳基亲核试剂的电子和空间效应的反应范围。观察到金（III）催化下三芳基丙二烯和二芳基茚的高收率。根据芳基亲核试剂的选择和反应温度的控制，可以获得不同的产物比例。或者，通过适当的炔丙基底物和两种不同的芳基亲核试剂的顺序一锅串联过程形成四芳基烯丙基目标产物。在相应的 N-卤代琥珀酰亚胺（NIS、NBS）存在下，以一锅法获得相应的卤代芳基产物（I 和 Br；高达 95%的 2-卤代二芳基茚）。
