A Route to Indoles via Modified Fischer Indole Intermediates from Sulfonanilides and Ketene Dithioacetal Monoxides

Kinoshita, Jun; Baralle, Alexandre; Yoshida, Akira; Yanagi, Tomoyuki; Nogi, Keisuke; Yorimitsu, Hideki

doi:10.1002/ajoc.202000397

Cited by 5 publications

(1 citation statement)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The reaction has a wide substrate scope, even N -sulfonylanilines such as 15 can be used to prepare indoles (Scheme 8 ). 48 ) This beautiful cascade process reminds us of the Fischer indole synthesis.…”

Section: Discovery Of a Cascade Of Interrupted Pummerer Reaction And ...mentioning

confidence: 90%

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Yorimitsu

Perry

2022

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Discovery Of a Cascade Of Interrupted Pummerer Reaction And ...mentioning

confidence: 90%

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Yorimitsu

Perry

2022

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

Self Cite

View full text Add to dashboard Cite

show abstract

Palladium‐Catalyzed C‐N Bond Formation: A Straightforward Alkoxymethylation Process for the Synthesis of the C1 and C3‐Dialkoxy Indoles

Guo

et al. 2020

ChemistrySelect

View full text Add to dashboard Cite

A novel approach for the synthesis of the C1 and C3‐dialkoxy indoles has been developed for using 2‐(phenylethynyl)aniline with formaldehyde and alcohols under the catalysis of acid and palladium acetate. This multicomponent reaction that provides a straightforward alkoxymethylation process to construct substituted indoles is expected to be an important method for the synthesis of indole derivatives.

show abstract

Dearomative di- and trifunctionalization of aryl sulfoxides via [5,5]-rearrangement

Liu

Liang

et al. 2022

Nat Commun

View full text Add to dashboard Cite

Aromatic [5,5]-rearrangement can in principle be an ideal protocol to access dearomative compounds. However, the lack of competent [5,5]-rearrangement impedes the advance of the protocol. In this Article, we showcase the power of [5,5]-rearrangement recently developed in our laboratory for constructing an intriguing dearomative sulfonium specie which features versatile and unique reactivities to perform nucleophilic 1,2- and 1,4-addition and cyclization, thus achieving dearomative di- and trifunctionalization of easily accessible aryl sulfoxides. Impressively, the dearomatization products can be readily converted to sulfur-removed cyclohexenones, naphthalenones, bicyclic cyclohexadienones, and multi-substituted benzenes. Mechanistic studies shed light on the key intermediates and the remarkable chemo-, regio- and stereoselectivities of the reactions.

show abstract

A Route to Indoles via Modified Fischer Indole Intermediates from Sulfonanilides and Ketene Dithioacetal Monoxides

Cited by 5 publications

References 72 publications

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Palladium‐Catalyzed C‐N Bond Formation: A Straightforward Alkoxymethylation Process for the Synthesis of the C1 and C3‐Dialkoxy Indoles

Dearomative di- and trifunctionalization of aryl sulfoxides via [5,5]-rearrangement

Contact Info

Product

Resources

About