Dephosphinylative [4 + 2] Benzannulation of Phosphinyl Ynamines: Application to the Modular Synthesis of Polycyclic Aromatic Amines,The Journal of Organic Chemistry

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Dephosphinylative [4 + 2] Benzannulation of Phosphinyl Ynamines: Application to the Modular Synthesis of Polycyclic Aromatic Amines
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2021-12-03 , DOI: 10.1021/acs.joc.1c01897
Yasuhiro Okuda ₁ , Mayo Fujimoto ₁ , Haruo Akashi ₂ , Akihiro Orita ₁

Affiliation

A series of 9-amino-10-halophenanthrenes were synthesized through a one-pot process, including dephosphinylative Sonogashira–Hagihara coupling of 2-bromobiphenyls with air-stable phosphinyl ynamines, followed by halonium-promoted [4 + 2] benzannulation of the resulting 2-(aminoethynyl)biphenyls. Nonsubstituted and methyl-substituted 2-bromobiphenyls rapidly underwent the Sonogashira–Hagihara aminoethynylation and the halogenative Friedel–Crafts benzannulation to provide the corresponding amino(halo)phenanthrenes in high yields, while electron-sufficient and -deficient substrates did slowly undergo the former and the latter to result in low yields, respectively. This protocol worked well for the syntheses of highly π-extended aminophenanthrenes and aminobenzonaphthothiophenes with different optical properties. Further application of this approach between 2,2″- and 2′,5′-dibromo-p-terphenyls with phosphinyl ynamines led to the regioselective formation of 6,13-diamino-5,12-dihalo- and 5,12-diamino-6,13-dihalo-dibenz[a,h]anthracenes via dual aminoethynylation and [4 + 2] benzannulation. The obtained analogues showed different ultraviolet–visible absorption and photoluminescence spectra with different emission quantum yields in CH₂Cl₂ solution and the powder state.

中文翻译：

膦酰氨基的脱膦[4 + 2]苯环化：在多环芳胺的模块化合成中的应用

通过一锅法合成了一系列 9-氨基-10-卤代菲，包括将 2-溴联苯与空气稳定的次膦酰炔胺脱膦酰化 Sonogashira-Hagihara 偶联，然后对所得产物进行卤化 [4 + 2] 苯环化2-(氨基乙炔基)联苯。未取代和甲基取代的 2-溴联苯迅速经历了 Sonogashira-Hagihara 氨基乙炔化和卤化 Friedel-Crafts 苯并化反应，以高产率提供相应的氨基（卤代）菲，而电子充足和电子不足的底物确实缓慢地经历了前者和后者分别导致低产量。该协议适用于合成具有不同光学特性的高度 π 扩展的氨基菲和氨基苯并萘噻吩。对三联苯与膦基炔胺通过双氨基乙炔化和 [4 + 2] 苯环化。_{得到的类似物在CH 2} Cl ₂溶液和粉末状态下显示出不同的紫外-可见吸收和光致发光光谱，具有不同的发射量子产率。

更新日期：2021-12-17

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