Mechanistic insights into hydroxy(tosyloxy)iodobenzene-mediated ditosyloxylation of chalcones: a DFT study

• Jai Parkash,
• Sangeeta Saini,
• Vaishali Saini,
• Omkar Bains and
• Raj Kamal

Beilstein J. Org. Chem. 2025, 21, 2703–2715, doi:10.3762/bjoc.21.208

• . However, the detailed mechanism for the formation of β,β-ditosyloxy ketones is different and depends on the nature of the substituent. Broadly, the formation of β,β-ditosyloxy ketones involves electrophilic addition followed by 1,2-aryl migration. Our study shows that the presence of an electron-donating

• group on the migrating aryl ring favours the formation of β,β-ditosyloxy ketones while in case of electron-withdrawing groups, there are nearly equal chances of the formation of α,β-ditosyloxy ketones and β,β-ditosyloxy ketones. Keywords: 1,2-aryl-migration; chalcones; ditosyloxylation; HTIB; para

• cationic intermediate which facilitates 1,2-aryl migration [20][21][22][23]. Similar types of oxidative rearrangements in α,β-unsaturated diaryl ketones that leads to the α-aryl-β,β dioxygenated skeleton via 1,2-aryl migration have been studied by using different reagents such as Tl(OCOCH3)3/CH3OH, Tl(ONO2

Hypervalent iodine-mediated intramolecular alkene halocyclisation

• Charu Bansal,
• Oliver Ruggles,
• Albert C. Rowett and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258

• , including ligand coupling, oxidative addition, intermolecular nucleophilic attack, 1,2-aryl migration, reductive elimination, and intramolecular nucleophilic attack. This approach offers a rapid and effective way to produce 5-fluoro-2-aryloxazoline compounds, which are valuable building blocks in organic

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

A survey of chiral hypervalent iodine reagents in asymmetric synthesis

• Soumen Ghosh,
• Suman Pradhan and
• Indranil Chatterjee

Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107

•  16, upper part) [57][58]. The reaction proceeds via the formation of the phenyliodinate intermediate 82 followed by a stereoselective 1,2-aryl migration. Elegantly, they utilized the 1,2-aryl migration approach to develop an enantioselective oxidative rearrangement of 1,1-disubstituted olefins 83

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• Scheme 10. β-Trifluoromethyl ketones could also be obtained from allylic alcohols 25 by a cascade trifluoromethylation/1,2-aryl migration. Yang, Xia and co-workers employed sodium triflinate under metal-free conditions with ammonium persulfate as the oxidant that was necessary to generate the CF3 radical

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

• Chinmay A. Shukla and
• Amol A. Kulkarni

Beilstein J. Org. Chem. 2017, 13, 960–987, doi:10.3762/bjoc.13.97

• equiv) in DMF solution and ICI as the promoter (3 equiv) in n-PrOH and was subjected to an oxidative 1,2-aryl migration. The reaction is carried out in a coiled reactor at 90 °C and 1 min residence time. The outlet stream is subjected to an alkaline solution of 2-mercaptoethanol, which quenched the ICI

The digital code driven autonomous synthesis of ibuprofen automated in a 3D-printer-based robot

• Philip J. Kitson,
• Stefan Glatzel and
• Leroy Cronin

Beilstein J. Org. Chem. 2016, 12, 2776–2783, doi:10.3762/bjoc.12.276

• (triflic) acid (CF3SO3H) as the Lewis acid catalyst to yield 4-isobutylpropiophenone (2). Once this is complete a solution of di(acetoxy)phenyl iodide (PhI(OAc)2) and trimethyl orthoformate (TMOF) in methanol (MeOH) is added to the reaction mixture in order to induce a 1,2-aryl migration to produce the

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H)-ones and isoquinoline-1,3(2H,4H)-diones

• Ping Qian,
• Bingnan Du,
• Wei Jiao,
• Haibo Mei,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2016, 12, 301–308, doi:10.3762/bjoc.12.32

• [18][19], decarboxylative alkenylation of cycloalkanes with aryl vinylic carboxylic acids [20][21], trifluoromethylthiolation [22], thiolation [23][24], alkenylation [25][26], dehydrogenation−olefination and esterification [27][28], radical addition/1,2-aryl migration [29], cascade alkylation

The synthesis of active pharmaceutical ingredients (APIs) using continuous flow chemistry

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134

• (Friedel–Crafts acylation, 1,2-aryl migration and saponification) this report focuses on improved output by intensifying the overall sequence (Scheme 3). As such an in-line extraction is performed after the Friedel–Crafts acylation step, followed by dissolving intermediate 18 in trimethyl orthoformate and

• DMF. This stream is then combined with a stream of ICl (21) to affect the 1,2-aryl migration in a heated flow reactor (1 min, 90 °C) followed by treatment of the stream with NaOH, 2-mercaptoethanol, MeOH and water in order to hydrolyse the intermediate methyl ester and quench residual ICl. After

• -aryl migration step. This was mediated by a hypervalent iodine reagent, PhI(OAc)2 (13), conducted in trimethyl orthoformate (14, TMOF) and methanol (Scheme 2). The direct saponification of the resulting rearranged methyl ester with an excess of base thus completed the telescoped flow synthesis of

Isotopic labelling studies for a gold-catalysed skeletal rearrangement of alkynyl aziridines

• Paul W. Davies,
• Nicolas Martin and
• Neil Spencer

Beilstein J. Org. Chem. 2011, 7, 839–846, doi:10.3762/bjoc.7.96

• the trend was consistent with that expected for a 1,2-aryl shift, the more complex mechanism also accounts for the observed outcomes. An increasingly electron-rich aryl group will favour both formation of benzylic cation I and 1,2-aryl migration from B, leading to the same products from each route