The Interrupted Pummerer Reaction: Design of Sulfoxides and Their Utility in Organic Synthesis

Higuchi, Kazuhiro; Tayu, Masanori

doi:10.3987/rev-20-935

Cited by 19 publications

(8 citation statements)

References 120 publications

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“…It was when we had been exploring the use of ketene dithioacetal monoxides (KDMs) for extended Pummerer reactions 22 – 32 ) that we accidentally realized the sigmatropic rearrangement of sulfur-tethered intermediates. As described in Scheme 4 , treatment of KDM 1 with trifluoromethanesulfonic anhydride (Tf 2 O, Tf = CF 3 SO 2 ) results in activation of the sulfoxide moiety of 1 .…”

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

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

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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“…The reactions begin with activation of the sulfoxide 1 with an acid anhydride (e.g., trifluoroacetic anhydride (TFAA) or triflic anhydride (Tf 2 O)). This enhances the electrophilicity of the sulfur center, allowing attack by the phenolic oxygen of 2 in an interrupted Pummerer reaction with I . − The resulting cationic intermediate II then undergoes a dearomative, charge-accelerated [3,3] sigmatropic rearrangement to form the key C–C bond. − Finally, deprotonation/tautomerization induces global rearomatization and provides the desired cross-coupled product 3 .…”

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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“…1 H-NMR (600 MHz, CDCl 3 ): 6.63 (d, J = 9.7, 0.25H, minor), 6.48 (d, J = 9.6, 0.75H, major), 6.10 -6.03 (m, 1H), 4.14 -4.06 (m, 2H), 3.77 -3.71 (m, 3H), 3.54-3.50 (m, 2H), 3.41-3. 35…”

Section: Methyl (2r3r6s7s)-3-((6-chlorohexyl)thio)-2cyano-7-(2-ethoxy...mentioning

confidence: 99%

“…In the past few years, we have devoted to the development of sulfonium‐rearrangements and the rearrangement triggered dearomatization reactions [22–38] . In this line of work, a [5,5]‐rearrangement triggered dearomatization of aryl sulfoxides recently developed in our laboratory allows the introduction of allyl nitriles and various nucleophiles to arene rings, and thus providing value‐added alicyclic compounds ( Scheme 1 ,B ) [26] .…”

Section: Introductionmentioning

confidence: 99%

“…In the past few years, we have devoted to the development of sulfonium-rearrangements and the rearrangement triggered dearomatization reactions. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] In this line of work, a [5,5]-rearrangement triggered dearomatization of aryl sulfoxides recently developed in our laboratory allows the introduction of allyl nitriles and various nucleophiles to arene rings, and thus providing value-added alicyclic compounds (Scheme 1,B). [26] In this article, we describe our efforts in combining the [5,5]-rearrangement triggered dearomatization with a stepwise [2 + 2]-cycloaddition to construct the tricyclo[4.2.1.0 3,8 ]nonane skeleton (Scheme 1,C).…”

Section: Introductionmentioning

confidence: 99%

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Construction of Cyclobutane‐Centered Tricyclic Caged Skeleton through a [5,5]‐Rearrangement Triggered Cascade

Hu,

Zhu,

et al. 2023

Helvetica Chimica Acta

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In this report, we describe the combination of [5,5]‐rearrangement‐triggered dearomatization recently developed in our laboratory with an intramolecular formal [2+2]‐cycloaddition for constructing an intriguing polysubstituted tricyclo[4.2.1.03,8]nonane derivatives. The synthesis features the use of simple and readily available three distinct starting materials including aryl sulfoxides, allyl nitriles, and certain nucleophiles or dienes which directly enriches the diversity of target molecules. This study provides an entirely new protocol for the synthesis of cyclobutane‐centered tricyclic caged skeleton.

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The Interrupted Pummerer Reaction: Design of Sulfoxides and Their Utility in Organic Synthesis

Cited by 19 publications

References 120 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

Construction of Cyclobutane‐Centered Tricyclic Caged Skeleton through a [5,5]‐Rearrangement Triggered Cascade

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