Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

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

Biaryl, C–h/c–h coupling, Interrupted pummerer reaction, Sigmatropic rearrangement, Sulfur

10.2183/pjab.98.012

0386-2208

190-205

Yorimitsu, Hideki

a2c027b0-9559-4027-be32-39e601818a88

Perry, Gregory J.P.

766e7fc8-abf3-4d1e-9949-c1b3439a2185

11 April 2022

Yorimitsu, Hideki

a2c027b0-9559-4027-be32-39e601818a88

Perry, Gregory J.P.

766e7fc8-abf3-4d1e-9949-c1b3439a2185

Yorimitsu, Hideki and Perry, Gregory J.P. (2022) Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement. Proceedings of the Japan Academy Series B: Physical and Biological Sciences, 98 (4), 190-205. (doi:10.2183/pjab.98.012).

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Accepted/In Press date: 19 January 2022

Published date: 11 April 2022

Additional Information: Funding Information: Gregory J. P. Perry received his Master of Chemistry from the University of Liverpool (U.K.) in 2012. During his undergraduate studies, he carried out research under the supervision of Professor P. Andrew Evans. He then joined the group of Professor Igor Larrosa and was awarded his Ph.D. from the University of Manchester (U.K.) in 2016. His doctoral studies focused on the development of decarboxylative and C–H transformations for organic synthesis. In 2017, he moved to Professor Kenichiro Itami’s group at the Institute of Transformative Bio-Molecules, Nagoya University (Japan) where he worked on the preparation of small molecules for chemical biology. Greg then moved back to the University of Manchester (U.K.) in 2018 as a Lecturer in Organic Chemistry. During this time, he worked within the group of Professor David J. Procter whilst developing his own research themes. In 2021, Greg was awarded a JSPS Postdoctoral Fellowship to continue his research within the group of Professor Hideki Yorimitsu at Kyoto University (Japan). His current research interests include the application of sulfur (VI) compounds (e.g., sulfonamides, sulfones) in synthesis and the carboxylation/decarboxylation of organic molecules. Funding Information: Hideki Yorimitsu was born in Kochi Prefecture, Japan, in 1975 and graduated from the Faculty of Engineering, Kyoto University in 1997. He obtained his Ph.D. in 2002 from Kyoto University under the tutelage of Professor Koichiro Oshima by engaging in research on synthetic radical reactions in aqueous media. He then served as a JSPS postdoctoral fellow with Professor Eiichi Nakamura at the Department of Chemistry, the University of Tokyo, where he worked on the synthesis of 15O-labeled 2-deoxyglucose of 2-min half-life for PET imaging as well as chemical modifications of nanocarbons. Subsequently, he became Assistant Professor (2003) and Associate Professor (2008) in the Graduate School of Engineering, Kyoto University. In 2009, he moved to the Graduate School of Science, Kyoto University, where he was promoted to Full Professor in 2015. He was Project Leader of ACT-C (2012–2018) and is currently Project Leader of CREST (since 2019), supported by Japan Science and Technology Agency. He received the Chemical Society of Japan Award for Young Chemists in 2009, the Young Scientists’ Prize from MEXT in 2011, the Mukaiyama Award in 2016, the Negishi Award in 2018, the JSPS Prize in 2020, and the Japan Academy Medal in 2020. His research has always focused on the development of new organic transformations in order to create new molecules, phenomena, and concepts. Currently, he is interested in electron injection into unsaturated molecules to generate and use the resulting carbanion species for modern organic synthesis, in addition to sulfur-aided organic synthesis. Funding Information: H.Y. wishes to thank his co-workers, whose names appear on the cited articles, for making this chemistry possible. H.Y. thanks JSPS KAKENHI Grants (JP19H00895, JP18H04409, JP16H01149), JST CREST grant JPMJCR19R4, the Naito Foundation, and the Mitsubishi Foundation for financial support. G.J.P.P. is the recipient of a JSPS Postdoctoral Fellowship for Research in Japan (KAKENHI Grant Number JP21F21039). Publisher Copyright: © 2022 The Author(s). Published under the terms of the CC BYNC license https://creativecommons.org/licenses/by-nc/4.0/

Keywords: Biaryl, C–h/c–h coupling, Interrupted pummerer reaction, Sigmatropic rearrangement, Sulfur