利用电阳性典型元素激发态的光反应的开发

IF 0.2 4区 化学 Q4 CHEMISTRY, ORGANIC
Yuki Nagashima, Masanobu Uchiyama, Ken Tanaka
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引用次数: 0

摘要

光诱导反应作为一种研究基态上动力学或热力学上被禁止的反应的有力工具,受到了广泛的关注。然而,这些反应主要是通过使用电负性元素如C、O、N、卤素以及过渡金属来发展的。另一方面,揭示了硼(B)、硅(Si)、锡(Sn)等电正主族元素在激发态上的性质,形成了高活性和选择性的光诱导反应。对于二硼(B-B)试剂,我们设计了阴离子光吸收硼酸盐配合物,使末端炔在紫外线照射下发生四重硼化反应。对于锡基(Sn),我们发现在锡基阴离子的照射下会产生激发的三态锡基二自由基,这与传统试剂(阳离子、阴离子和自由基)具有正交性,可以实现炔的氢锡化和氟芳烃的去氟锡化。对于硅硼烷(Si-B)试剂,我们在不需要任何催化剂的情况下,通过激发硅硼酸盐配合物,开发了喹啉类化合物的脱芳三元素化(碳硅硼化)反应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
電気陽性な典型元素の励起状態を利用する光反応の開発
Photoinduced reactions have received much attention as a powerful tool to access kinetically or thermodynamically prohibited reactions on the ground state. However, these reactions have been developed mainly by using electro-negative elements such as C, O, N, halogens as well as transition-metals. On the other hand, we have revealed the nature of chemical species including electro-positive main-group elements, such as boron (B), silicon (Si), and tin (Sn), on the excited state, developing the highly reactive and selective photoinduced reactions. For diboron (B-B) reagents, we designed the anionic photo-absorbing borate complex to enable a quadruple borylation reaction of terminal alkynes under ultraviolet irradiation. For stannyl (Sn) species, we revealed that the illumination of stannyl anions generates the excited triplet stannyl diradicals, which showed the orthogonality to traditional reagents (cations, anions, and radicals) to enable hydrostannylation of alkynes and defluorostannylation of fluoroarenes. For silylborane (Si-B) reagents, we developed dearomative triple elementalization (carbo-silaboration) reactions of quinolines by the excitation of silyl-borate complexes without the need for any catalyst.
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来源期刊
CiteScore
0.30
自引率
0.00%
发文量
120
审稿时长
6-12 weeks
期刊介绍: Information not localized
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