Metal-free synthesis of biaryls from aryl sulfoxides and sulfonanilides via sigmatropic rearrangement

Yoshida, Akira; Okamoto, Koichi; Yanagi, Tomoyuki; Nogi, Keisuke; Yorimitsu, Hideki

doi:10.1016/j.tet.2020.131232

Cited by 7 publications

(4 citation statements)

References 68 publications

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“…After the screening of electron-withdrawing groups, sulfonyl groups were found to participate in the biaryl formation efficiently (similar to the indole synthesis in Scheme 8 ), and p -methoxybenzenesulfonyl group showed the best performance among those tested (Scheme 21 ). 80 ) While the scope of the reactions is not so wide as in the case of phenols, a range of heteroaryl sulfoxides and naphthyl sulfoxides reacted to yield sulfonylaminobiaryls 42 .…”

Section: Variations Of the Synthesis Of 2-hydroxy-2′-sulfanylbiphenylsmentioning

confidence: 99%

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Yorimitsu

Perry

2022

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

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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.

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Section: Variations Of the Synthesis Of 2-hydroxy-2′-sulfanylbiphenylsmentioning

confidence: 99%

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Yorimitsu

Perry

2022

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

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“…39,40 Using a carefully selected p-anisylsulfonyl (Ans) protecting group, a range of anilines 68 were coupled with (hetero)aryl sulfoxides 67. 39 The mechanism was suggested to proceed in a fashion similar to the coupling of sulfoxides and phenols (Scheme 2). When unprotected anilines 69 were used, the coupling was more challenging, which caused limitations in the scope.…”

Section: Cross-coupling Of Sulfoxides Withmentioning

confidence: 99%

“…Scheme ). , Using a carefully selected p -anisylsulfonyl (Ans) protecting group, a range of anilines 68 were coupled with (hetero)aryl sulfoxides 67 . The mechanism was suggested to proceed in a fashion similar to the coupling of sulfoxides and phenols (Scheme ).…”

Section: Cross-coupling Of Sulfoxides With Phenols and Related Transf...mentioning

confidence: 99%

Sulfur(IV) in Transition-Metal-Free Cross-Couplings for Biaryl Synthesis

Perry

Yorimitsu

2022

ACS Sustainable Chem. Eng.

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The reactivity of sulfur(IV) compounds is of great current interest among organic chemists. In this Perspective, we discuss the chemistry of sulfur(IV) (namely, sulfoxides, sulfonium salts, and sulfinates) within the area of transition-metal-free cross-couplings for biaryl synthesis. These sulfur(IV)-based methods show potential in sustainable biaryl formation and can deliver unique biaryl structures that are difficult to access by other means. This Perspective also highlights how the versatile reactivity of sulfur(IV) has helped design new reagents, mediators, and catalysts.

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“…According to the previous successes, the reaction of p ‐anisylsulfonyl‐protected p ‐toluidine 1 a with aryl KDM 2 a by means of trifluoroacetic anhydride was chosen as a model reaction. Treatment of 1 a and 2 a (1.5 equiv) with (CF 3 CO) 2 O (1.8 equiv) in toluene at −40 °C for 15 h provided the expected indole 3 aa in 77% yield (Table , entry 1).…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2020

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An SÀ N variant of the NÀ N-based Fischer indole synthesis has been developed. Treatment of sulfonanilides and ketene dithioacetal monoxides with a powerful acid anhydride provides N-sulfonyl-2-methylsulfanylindoles. The initial interrupted Pummerer reaction would yield the key SÀ N-tethered precursor in situ that then undergoes [3,3] sigmatropic rearrangement, after which the endgame to the indole ring follows the Fischer manner.

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Metal-free synthesis of biaryls from aryl sulfoxides and sulfonanilides via sigmatropic rearrangement

Cited by 7 publications

References 68 publications

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Sulfur(IV) in Transition-Metal-Free Cross-Couplings for Biaryl Synthesis

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

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