Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts.
Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts.
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多功能可见光驱动合成不对称膦和膦盐。
DOI：
10.1002/chem.202002646
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发表时间：
2020-12-09
期刊：
影响因子：
--
通讯作者：
Wolf R
中科院分区：
文献类型：
--
作者：
Arockiam PB;Lennert U;Graf C;Rothfelder R;Scott DJ;Fischer TG;Zeitler K;Wolf R
不对称取代的叔膦和季磷盐在工业和学术界广泛应用。尽管它们具有重要意义，但合成这些化合物的传统方法通常需要苛刻的反应条件、起始材料的预功能化、高度敏感的有机金属试剂或昂贵的过渡金属催化剂。因此，温和、实用的方法仍然是难以捉摸的，尽管目前有很大的兴趣。在这里，我们描述了一种可见光驱动的方法，从仲膦和伯膦形成这些产品。使用廉价的有机光催化剂和蓝光照射，芳基膦既可以烷基化，也可以使用市售的有机卤化物进行芳基化。此外，同样的有机催化剂可以在一个反应步骤中将白磷（P4）直接转化为对称的芳基膦和磷盐，这在以前只可能使用贵金属催化。光驱动：报道了一种温和而简便的光氧化还原方法用于不对称取代的膦和磷盐。用各种芳基和烷基碘化物、二异丙基乙胺（DIPEA）和有机光催化剂3DPAFIPN对一苯基和二苯基膦进行蓝光照射，可得到收率高至优异的所需产品。此外，同样的方法将白磷（P4）直接转化为对称的芳基膦和磷盐。
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition‐metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible‐light‐driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue‐light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis. Driven by light: A mild and facile photoredox approach towards asymmetrically substituted phosphines and phosphonium salts is reported. Blue‐light irradiation of mono‐ and diphenylphosphine with various aryl and alkyl iodides, diisopropylethylamine (DIPEA), and the organic photocatalyst 3DPAFIPN affords the desired products in good‐to‐excellent yields. In addition, the same method transforms white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts.
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影响因子：
16.6
作者：
Huang, Hongda;Deng, Zhong;Vladimirova, Olga;Wiedmer, Andreas;Lu, Fang;Lieberman, Paul M.;Patel, Dinshaw J.
通讯作者：
Patel, Dinshaw J.
影响因子：
4.3
作者：
Bugaenko, Dmitry, I;Volkov, Alexey A.;Karchava, Alexander, V
通讯作者：
Karchava, Alexander, V
影响因子：
4
作者：
IWAHASHI, H;ISHIKAWA, Y;KOYANO, K
通讯作者：
KOYANO, K
影响因子：
3.9
作者：
Bissessar, Damien;Egly, Julien;Achard, Thierry;Steffanut, Pascal;Bellemin-Laponnaz, Stephane
通讯作者：
Bellemin-Laponnaz, Stephane
影响因子：
4.9
作者：
Cassity, Cody G.;Mirjafari, Arsalan;Davis, James H., Jr.
通讯作者：
Davis, James H., Jr.