Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a <i>meta</i>-selective rearrangement

Maryasin, Boris; Kaldre, Dainis; Galaverna, Renan; Klose, Immo; Ruider, Stefan A.; Drescher, Martina; Kählig, Hanspeter; González, Leticia; Eberlin, Marcos N.; Jurberg, Igor D.; Maulide, Nuno

doi:10.1039/c7sc04736c

Cited by 33 publications

(19 citation statements)

References 49 publications

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“…Computational analysis revealed the new product to arise from an initial [3,3]-sigmatropic rearrangement onto the substituted ortho -carbon atom and a subsequent 1,2-alkyl shift, followed by rearomatization (Scheme 34c). 126…”

Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

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Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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“…In fact, the versatility of silane 26 is illustrated by the synthesis of the structurally diverse series 28 – 32 (Table A). For the ortho, ortho’ ‐disubstituted λ 3 ‐aryliodanes, the incoming group is redirected to the meta C−H position (product 33 ), in line with a [3,3]‐rearrangement followed by an ortho ‐to‐ meta [1,2]‐shift . As seen in Table B, the open‐chain sulfonylated allylsilane 34 was also reactive, providing the corresponding ortho coupling product 35 in 92 % yield.…”

Section: Methodsmentioning

confidence: 98%

Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization

Bouvet

Izquierdo

et al. 2018

Angewandte Chemie

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Among halogenated aromatics,i odoarenes are unique in their ability to produce the bench-stable halogen(III) form. Earlier,s uch iodine(III) centers were shown to enable CÀHf unctionalization ortho to iodine via halogen-centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane-directed para C À Hbenzylation, as well as by developing an efficient C À Hc oupling with sulfonyl-substituted allylic silanes.T hrough the combination of the one-shot nature of the coupling event and the iodine retention, multisubstituted arenes can be prepared by sequentially engaging up to three aromatic CÀH sites.T his type of iodine-based iterative synthesis will serve as atool for the formation of value-added aromatic cores. Scheme 1. Selected precedentsiniodane-and sulfoxide-directed CÀH functionalization.

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“…Recently, Maulide has reported that this kind of rearrangement is on the borderline between concerted and stepwise mechanisms. [9] However, research focusing on the nature of the charge-accelerated sigmatropic rearrangement of arylsulfonium species remains limited.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Investigation of a Synthetic Route to Biaryls by the Sigmatropic Rearrangement of Arylsulfonium Species

Yanagi

Yorimitsu

2021

Chemistry A European J

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A comprehensive mechanistic investigation was conducted on the coupling reaction of aryl sulfoxides with phenols by using trifluoroacetic anhydride to yield biaryls. NMR experiments revealed that our previously proposed mechanism, which consists of a cascade of an interrupted Pummerer reaction and a rate-determining [3,3] sigmatropic rearrangement, is reasonable. The electronic effects of the substrates were also evaluated to elucidate the nature of the rearrangement step. Based on experimental observations and theoretical calculations, we conclude that the rearrangement is highly asynchronous and stepwise rather than concerted when electron-rich phenols are employed for the reaction.

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Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement

Abstract: A mechanistic investigation of the acid-catalysed redox-neutral arylation of ynamides intertwining ESI-MS, DFT and experiments reveals diverse pathways available from an otherwise simple-looking transformation.

Cited by 33 publications

References 49 publications

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization

Mechanistic Investigation of a Synthetic Route to Biaryls by the Sigmatropic Rearrangement of Arylsulfonium Species

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