From perfluoroalkyl aryl sulfoxides to ortho thioethers

• Yang Li,
• Guillaume Dagousset,
• Emmanuel Magnier and
• Bruce Pégot

Beilstein J. Org. Chem. 2024, 20, 2108–2113, doi:10.3762/bjoc.20.181

• , sigmatropic rearrangements have established themselves as robust and versatile tools for many transformations in organic synthesis [1][2][3]. They were widely employed with a wide range of substrates. With a peculiar type of scaffold, S-perfluoroalkyl aryl sulfoxides, in 2009, we were the first to demonstrate

α,γ-Dioxygenated amides via tandem Brook rearrangement/radical oxygenation reactions and their application to syntheses of γ-lactams

• Mikhail K. Klychnikov,
• Radek Pohl,
• Ivana Císařová and
• Ullrich Jahn

Beilstein J. Org. Chem. 2021, 17, 688–704, doi:10.3762/bjoc.17.58

• -containing skeletons of the general structure IX or XI, respectively (Scheme 1A). Recently, we became interested in merging sigmatropic rearrangements with radical oxygenation reactions since profound changes in the connectivity patterns during both reaction modes will potentially significantly simplify the

Tuneable access to indole, indolone, and cinnoline derivatives from a common 1,4-diketone Michael acceptor

• Dalel El-Marrouki,
• Sabrina Touchet,
• Abderrahmen Abdelli,
• Hédi M’Rabet,
• Mohamed Lotfi Efrit and
• Philippe C. Gros

Beilstein J. Org. Chem. 2020, 16, 1722–1731, doi:10.3762/bjoc.16.144

• antibacterial, antifungal, anticancer, or anti-inflammatory agents or even on the central nervous system [7][12][13]. Several routes have been reported to access these key compounds, the most developed being for the indole [14] derivatives using the Fischer indole synthesis involving sigmatropic rearrangements

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

• Katarzyna Włodarczyk,
• Piotr Borowski and
• Marek Stankevič

Beilstein J. Org. Chem. 2020, 16, 88–105, doi:10.3762/bjoc.16.11

• -Brook ([1,2]-rearrangement) [38][39][40][41][42], and [2,3]-sigmatropic rearrangements of propargyl and allylphosphinites [43][44][45][46]. Other [1,2]-rearrangements include α,β-epoxyphosphonate opening [47], β-halo-α-hydroxyphosphonate rearrangement [48], phosphirene rearrangement [49], or the unusual

Why do thioureas and squaramides slow down the Ireland–Claisen rearrangement?

• Dominika Krištofíková,
• Juraj Filo,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2019, 15, 2948–2957, doi:10.3762/bjoc.15.290

• acid, catalyzed by in situ-generated copper hydride with diethoxymethylsilane as a reductive agent gave the γ,δ-unsaturated acid with good to excellent diastereoselectivities [27]. Various asymmetric organocatalyzed rearrangements are known [28]. However, the catalysis of sigmatropic rearrangements is

• difficult due to their rather nonpolar transition states, which are difficult to be addressed by catalysts [29]. Several stereoselective [3,3]-sigmatropic rearrangements are realized with chiral Brønsted acids [30][31][32][33][34]. Jacobsen reported guanidinium-catalyzed enantioselective Claisen

• for this difference, however, remains unclear. The explanation may be connected to a more compact transition state of sigmatropic rearrangements than their starting materials, which is thus less amenable to additional stabilization via hydrogen-bonding catalysts. To get further insight, we have

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

• Guillaume Ernouf,
• Jean-Louis Brayer,
• Christophe Meyer and
• Janine Cossy

Beilstein J. Org. Chem. 2019, 15, 333–350, doi:10.3762/bjoc.15.29

• through different strategies, this review is focusing specifically on the use of [2,3]- and [3,3]-sigmatropic rearrangements involving cyclopropenylcarbinol derivatives as substrates. These sigmatropic rearrangements, which have been developed in recent years, allow a remarkably efficient and

• stereoselective access to a wide variety of heterosubstituted and/or functionalized alkylidenecyclopropanes which would not be readily accessible by other strategies. The different [2,3]- and [3,3]-sigmatropic rearrangements of cyclopropenylcarbinol derivatives disclosed to date, as well as the analysis of their

• substrate scope and some applications of the products arising from those reactions, are presented in this review. Keywords: alkylidenecyclopropanes; cyclopropanes; cyclopropenes; sigmatropic rearrangements; strained rings; Introduction Among the ever expanding diversity of chemical transformations

Synthesis of 1,2-divinylcyclopropanes by metal-catalyzed cyclopropanation of 1,3-dienes with cyclopropenes as vinyl carbene precursors

• Jesús González,
• Alba de la Fuente,
• María J. González,
• Laura Díez de Tejada,
• Luis A. López and
• Rubén Vicente

Beilstein J. Org. Chem. 2019, 15, 285–290, doi:10.3762/bjoc.15.25

• allows sigmatropic rearrangements leading to odd-numbered carbocyclic derivatives [8]. In this sense, seven-membered carbocycles, namely 1,4-cycloheptadienes, can be forthrightly prepared from cis- or trans-1,2-divinylcyclopropanes through a Cope rearrangement [8][9]. The potential of this type of

Are boat transition states likely to occur in Cope rearrangements? A DFT study of the biogenesis of germacranes

• José Enrique Barquera-Lozada and
• Gabriel Cuevas

Beilstein J. Org. Chem. 2017, 13, 1969–1976, doi:10.3762/bjoc.13.192

• Cope sigmatropic rearrangements. Normally, this reaction proceeds through a transition state with a chair conformation. However, the transformation of schkuhriolide (germacrane) into elemanschkuhriolide (elemane) may occur through a boat transition state due to the final configuration of the

Tandem processes promoted by a hydrogen shift in 6-arylfulvenes bearing acetalic units at ortho position: a combined experimental and computational study

• Mateo Alajarin,
• Marta Marin-Luna,
• Pilar Sanchez-Andrada and
• Angel Vidal

Beilstein J. Org. Chem. 2016, 12, 260–270, doi:10.3762/bjoc.12.28

• construction of diverse fused ring systems. Other classical pericyclic processes that may potentially occur in fulvene fragments (electrocyclic and ene reactions, sigmatropic rearrangements and shifts) have received less attention, most probably with the only exception of the Claisen rearrangement [16

Synthesis of Xenia diterpenoids and related metabolites isolated from marine organisms

• Tatjana Huber,
• Lara Weisheit and
• Thomas Magauer

Beilstein J. Org. Chem. 2015, 11, 2521–2539, doi:10.3762/bjoc.11.273

• commonly employed method for the synthesis of cyclononenes due to the predictability of the stereochemical outcome of the product. The construction of cyclononenes can furthermore be achieved by thermal [3,3]-sigmatropic rearrangements of 1,5-dienes C. When the reaction proceeds via a chairlike transition

• , several strategies for the preparation of the characteristic nine-membered carbocyclic ring structures have been developed. The synthetic strategies are typically based on ring expansion (Grob-type fragmentation and sigmatropic rearrangements), ring closing (metathesis and transition metal-catalyzed

Anionic sigmatropic-electrocyclic-Chugaev cascades: accessing 12-aryl-5-(methylthiocarbonylthio)tetracenes and a related anthra[2,3-b]thiophene

• Laurence Burroughs,
• John Ritchie,
• Mkhethwa Ngwenya,
• Dilfaraz Khan,
• William Lewis and
• Simon Woodward

Beilstein J. Org. Chem. 2015, 11, 273–279, doi:10.3762/bjoc.11.31

• via nominal [3,3]-sigmatropic rearrangements of xanthates. As the thiocarbamate products derived from these are predicted to be easily hydrolised to thiolates this potentially offers a simple route to a protected SH analogue of 3. Lin’s chemistry [14] cannot be used as no simple method to modify SOPh

• to SH is available. We proposed that use of starting material xanthate 1c should provide suitably protected 5-thiotetracene derivatives directly (Scheme 2). The required [3,3]-sigmatropic rearrangements and subsequent 6π elecrocyclisations of 1c have precise stereochemical requirements (Scheme 2

• reaction components maximises the yield of 7a (Table 1, runs 3–6). These results very strongly suggest unprecedented anionic [3,3]-sigmatropic rearrangement starting from 1d; another addition to the body of evidence for the importance of charge upon sigmatropic rearrangements [25][26]. In the subsequent

Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

• Peter A. Wade,
• Alma Pipic,
• Matthias Zeller and
• Panagiota Tsetsakos

Beilstein J. Org. Chem. 2013, 9, 2137–2146, doi:10.3762/bjoc.9.251

• 3 to 19 by [3,3]-sigmatropic rearrangements (vide infra). Sn(IV)-catalyzed reactions of nitronic esters The possibility that ternary adduct 12a,b could arise from ring opening of one of the nitronic esters was considered. Neither nitronic ester 4 nor 7 afforded 12a,b when treated with tin(IV

Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

• Jungho Jun,
• Hyu-Suk Yeom,
• Jun-Hyun An and
• Seunghoon Shin

Beilstein J. Org. Chem. 2013, 9, 1724–1729, doi:10.3762/bjoc.9.198

• -substituent, the steric nature of R2 and R3 substituents determined the ratio of [3,3]- versus [1,3]-products. Finally, R4 substituent at the allyl group (2n) retarded the transformation severely, indicating an unfavorable steric interaction. Unlike previous intramolecular [3,3]-sigmatropic rearrangements [13

• with a lower amount of the excess reactant. However, it is accompanied by a significant amount of byproduct(s) such as 4 and 5, resulting from the dissociation of the allyl C–O cleavage. While the linear allyl ethers preferred [3,3]-sigmatropic rearrangements, the presence of an α-substituent led to a

Highly efficient gold(I)-catalyzed Overman rearrangement in water

• Dong Xing and
• Dan Yang

Beilstein J. Org. Chem. 2011, 7, 781–785, doi:10.3762/bjoc.7.88

• have been used for different types of [3,3]-sigmatropic rearrangements [14][15], only Pd(II) and Hg(II) salts have found wide application in Overman rearrangements. In recent years, gold catalysts have been successfully applied to a series of [3,3]-sigmatropic rearrangements, such as the rearrangement

Enantiospecific synthesis of [2.2]paracyclophane- 4-thiol and derivatives

• Gareth J. Rowlands and
• Richard J. Seacome

Beilstein J. Org. Chem. 2009, 5, No. 9, doi:10.3762/bjoc.5.9

• ], sigmatropic rearrangements [21] and as either thiyl radical precursors [22] or as a source of hydrogen in radical chemistry [23]. With the appropriate sulfur derivative, stereoselective variants of all these transformations can be envisaged. Currently, there are few examples of sulfur containing [2.2