- 著者
- Hideki YORIMITSU Gregory J. P. PERRY
- 出版者
- The Japan Academy
- 雑誌
- Proceedings of the Japan Academy, Series B (ISSN:03862208)
- 巻号頁・発行日
- vol.98, no.4, pp.190-205, 2022-04-11 (Released:2022-04-11)
- 参考文献数
- 83
- 被引用文献数
- 10
Biaryl synthesis continues to occupy a central role in chemical synthesis. From blockbuster drug molecules to organic electronics, biaryls present numerous possibilities and new applications continue to emerge. Transition-metal-catalyzed coupling reactions represent the gold standard for biaryl synthesis and the mechanistic steps, such as reductive elimination, are well established. Developing routes that exploit alternative mechanistic scenarios could give unprecedented biaryl structures and expand the portfolio of biaryl applications. We have developed metal-free C–H/C–H couplings of aryl sulfoxides with phenols to afford 2-hydroxy-2′-sulfanylbiaryls. This cascade strategy consists of an interrupted Pummerer reaction and [3,3] sigmatropic rearrangement. Our method enables the synthesis of intriguing aromatic molecules, including oligoarenes, enantioenriched dihetero[8]helicenes, and polyfluorobiaryls. From our successes in aryl sulfoxide/phenol couplings and a deeper understanding of sigmatropic rearrangements for biaryl synthesis, we have established related methods, such as aryl sulfoxide/aniline and aryl iodane/phenol couplings. Overall, our fundamental interests in underexplored reaction mechanisms have led to various methods for accessing important biaryl architectures.
- 著者
- Jing-Dong Guo Takahiro Sasamori Yutaro Yamamoto Hiroshi Matsubara Shigeru Nagase Hideki Yorimitsu
- 出版者
- (社)日本化学会
- 雑誌
- Bulletin of the Chemical Society of Japan (ISSN:00092673)
- 巻号頁・発行日
- pp.20150343, (Released:2015-11-16)
- 被引用文献数
- 4
The previously reported palladium-catalyzed silylation of aryl chlorides with silylsilatranes were theoretically reinvestigated by DFT calculations with a focus on the effect of the transannular Si–N coordination on silyl transfer. The Si–N coordination proved to be not so influential as to accelerate the silyl transfer. However, it should be of benefit to use silylsilatranes as silylating agents because of their easy handling and facile preparation.