Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• angle of 176°, explaining the preference for the different skeletal rearrangements in the two possible configurations at C4 in these rigid ring systems [19][21]. The involvement of the ring-oxygen in nucleophilic displacement reactions in 1,6-anhydroglucose derivatives has also been invoked to explain

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• indicative of a carbocationic pathway are not observed, suggesting that RPC does not occur. Further, the inability of ATRA products to undergo SN2 with the added nucleophiles under our reaction conditions is inconsistent with a tandem ARTA/nucleophilic displacement alternative mechanism. Finally, a

Retraction: One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea

• Mohammad Abbasi and
• Reza Khalifeh

Beilstein J. Org. Chem. 2023, 19, 1170–1170, doi:10.3762/bjoc.19.85

• Mohammad Abbasi Reza Khalifeh Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran Department of Chemistry, Shiraz University of Technology, Shiraz, Iran 10.3762/bjoc.19.85 Keywords: benzoic anhydride; Michael addition; nucleophilic displacement; thioester

Synthesis and characterisation of new antimalarial fluorinated triazolopyrazine compounds

• Kah Yean Lum,
• Jonathan M. White,
• Daniel J. G. Johnson,
• Vicky M. Avery and
• Rohan A. Davis

Beilstein J. Org. Chem. 2023, 19, 107–114, doi:10.3762/bjoc.19.11

• ethanol using the standard nucleophilic displacement method as previously described (Scheme 1) [14][16]. Structures of synthesised compounds 4–9 were determined using 1D/2D NMR and HRMS (Supporting Information File 1, S6–S23). Crystals of compounds 5 and 6 were also analysed by X-ray crystallography

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

• Vladislav A. Budevich,
• Sergei V. Voitekhovich,
• Alexander V. Zuraev,
• Vadim E. Matulis,
• Vitaly E. Matulis,
• Alexander S. Lyakhov,
• Ludmila S. Ivashkevich and
• Oleg A. Ivashkevich

Beilstein J. Org. Chem. 2021, 17, 385–395, doi:10.3762/bjoc.17.34

• thermal stability of the tetrazolium-5-aminides (see Supporting Information File 1 for more details). Some nucleophilic displacement reactions were carried out in order to show the higher reactivity of the aminides in comparison to the parent aminotetrazoles. The high nucleophilicity of the imine group in

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• widely applied till now. The development of this method before 1965 was reviewed by Sander [12] and this review contains new advances since 1965. After Sander’s review [12], Cerny and Polacek reported the synthesis of a thietane derivative via the double nucleophilic displacement of 1,3-dichloroalkane in

• -galactopyranoside (93)) from methyl α-D-glucopyranoside (90) through a Mitsunobu thioacetylation, mesylation, thioacetate hydrolysis with the treatment of sodium bicarbonate, and a subsequent intramolecular nucleophilic displacement. In the displacement step, the formation of the four-membered thietane ring is

• was first converted to the oxirane-fused derivative 98 through an intramolecular substitution. After hydrolysis, the thiolate underwent an intramolecular nucleophilic displacement to generate the final thietane-fused α-D-gulopyranoside 100 [50] (Scheme 21). In 2004, Schulze and co-workers synthesized

An improved, scalable synthesis of Notum inhibitor LP-922056 using 1-chloro-1,2-benziodoxol-3-one as a superior electrophilic chlorinating agent

• Nicky J. Willis,
• Elliott D. Bayle,
• George Papageorgiou,
• David Steadman,
• Benjamin N. Atkinson,
• William Mahy and
• Paul V. Fish

Beilstein J. Org. Chem. 2019, 15, 2790–2797, doi:10.3762/bjoc.15.271

• POCl3 to give 9. Finally, nucleophilic displacement of the C4–Cl of 9 by methyl thioglycolate (13) gave ester 10 which was hydrolysed with NaOH to afford 1. This route has been reliably performed on large scale to produce multigram quantities of 1 in good efficiency (total yield over 8-steps from 3: 18

N-(1-Phenylethyl)aziridine-2-carboxylate esters in the synthesis of biologically relevant compounds

• Iwona E. Głowacka,
• Aleksandra Trocha,
• Andrzej E. Wróblewski and
• Dorota G. Piotrowska

Beilstein J. Org. Chem. 2019, 15, 1722–1757, doi:10.3762/bjoc.15.168

• (Scheme 32) [85]. The reaction involved a nucleophilic displacement at more hindered C2 with inversion of configuration to form the azido ester (2S,1'R)-126 which was transformed into (S)-125 in usual way. However, since amines can be obtained from azides by a Staudinger reaction the ester (2S,1'R)-126

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

• Antonella Di Vincenzo,
• Antonio Palumbo Piccionello,
• Alberto Spinella,
• Delia Chillura Martino,
• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2019, 15, 633–641, doi:10.3762/bjoc.15.59

• of Palermo – V.le delle Scienze, Ed. 18, 90128 Palermo, Italy Istituto per lo Studio dei Materiali Nanostrutturati (ISMN), CNR Palermo – Via Ugo La Malfa 153, 90146 Palermo, Italy 10.3762/bjoc.15.59 Abstract Two mixtures of polyaminoazides were synthesized by a nucleophilic displacement strategy

• their relative amount as well. Hence, keeping into account the structures of the precursor species, by means of a simple combinatorial analysis it is possible to show how each component is indeed the product of simple nucleophilic displacement processes. The HR-ESIMS spectra of both mixtures appear very

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

• leading to zwitterronic intermediates 8 and 8’. This would result in an increase of conformational flexibility thereby facilitating the nucleophilic displacement of the ammonium by the phosphinite through transition states TS1 and TS2 (SN2-type process), respectively. Oxaphospholanium zwitterions 9 and 9

One-pot synthesis of epoxides from benzyl alcohols and aldehydes

• Edwin Alfonzo,
• Jesse W. L. Mendoza and
• Aaron B. Beeler

Beilstein J. Org. Chem. 2018, 14, 2308–2312, doi:10.3762/bjoc.14.205

• ]. Despite these efforts, the synthesis of epoxides using this powerful transformation still often requires multiple steps due to the need to independently synthesize the sulfonium salt. Typically, the salt is synthesized from nucleophilic displacement of benzyl halides but the work by Aggarwal and co

Phosphoramidite building blocks with protected nitroxides for the synthesis of spin-labeled DNA and RNA

• Timo Weinrich,
• Eva A. Jaumann,
• Ute M. Scheffer,
• Thomas F. Prisner and
• Michael W. Göbel

Beilstein J. Org. Chem. 2018, 14, 1563–1569, doi:10.3762/bjoc.14.133

• , for example, nucleophilic displacement by 4-amino-TEMPO has been used to prepare RNA strands containing the cytidine derivative 1 and its adenosine analog 3 [8][25][26] (Figure 1). Alternatively, by adapting the standard synthetic procedures, nitroxides can be directly incorporated into

Hyper-reticulated calixarene polymers: a new example of entirely synthetic nanosponge materials

• Alberto Spinella,
• Marco Russo,
• Antonella Di Vincenzo,
• Delia Chillura Martino and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2018, 14, 1498–1507, doi:10.3762/bjoc.14.127

• ], by a nucleophilic aromatic displacement reaction between p-fluoronitrobenzene and the proper amine. Alkyl diazides A1–A4 were obtained by a trivial nucleophilic displacement reaction between the proper alkyl dihalide and sozium azide, according to the following procedure. The proper alkyl dihalide

Phosphodiester models for cleavage of nucleic acids

• Satu Mikkola,
• Tuomas Lönnberg and
• Harri Lönnberg

Beilstein J. Org. Chem. 2018, 14, 803–837, doi:10.3762/bjoc.14.68

• dissociative nature, respectively. The pentacoordinated species, called pentaoxyphosphorane, may also have a sufficiently long life-time to represent a minimum on the energy profile. The reaction then proceeds in a stepwise manner. It is an associative nucleophilic displacement (AN + DN) with late transition

AuBr₃-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars

• Jayashree Rajput,
• Srinivas Hotha and
• Madhuri Vangala

Beilstein J. Org. Chem. 2018, 14, 682–687, doi:10.3762/bjoc.14.56

• ], glycoconjugates [30][31][32], N-glycosyl heterocycles [33][34], N-glycosyl triazole [35][36], etc. Glycosyl azides can be accessed from the corresponding glycosyl halides [37][38][39][40] by nucleophilic displacement with NaN3 or using trimethylsilyl azide in the presence of a phase transfer catalyst [41][42][43

Continuous multistep synthesis of 2-(azidomethyl)oxazoles

• Thaís A. Rossa,
• Nícolas S. Suveges,
• Marcus M. Sá,
• David Cantillo and
• C. Oliver Kappe

Beilstein J. Org. Chem. 2018, 14, 506–514, doi:10.3762/bjoc.14.36

• continuous-flow process. The general synthetic strategy involves a thermolysis of vinyl azides to generate azirines, which react with bromoacetyl bromide to provide 2-(bromomethyl)oxazoles. The latter compounds are versatile building blocks for nucleophilic displacement reactions as demonstrated by their

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• sodium hydroxide solution at ambient temperature. The methylthio group was converted to benzoylguanidino derivative 203 by nucleophilic displacement with ammonia in DMF on vigorous heating in a sealed tube. Subsequently, compounds 203 were converted to 6-amino-2-substituted-2H-pyrazolo[3,4-d]pyrimidin-4

Conformational preferences of α-fluoroketones may influence their reactivity

• Graham Pattison

Beilstein J. Org. Chem. 2017, 13, 2915–2921, doi:10.3762/bjoc.13.284

• proceed cleanly, with minimal byproduct formation, and in the case of examining the reactivity of the carbonyl group of α-halogenated ketones, should show very high regioselectivity for nucleophilic addition to the carbonyl group rather than nucleophilic displacement of the halogen atom. Another important

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

• Marco Russo,
• Daniele La Corte,
• Annalisa Pisciotta,
• Serena Riela,
• Rosa Alduina and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2751–2763, doi:10.3762/bjoc.13.271

• reacting a heptakis(6-deoxy-6-halo)-β-CD with an excess of a suitable polyamine [37]. The reaction leads to the exhaustive nucleophilic displacement of the halogen atoms on the starting material [38][39]. However, the products obtained constitute complex mixtures of various inseparable derivatives, having

Vinylphosphonium and 2-aminovinylphosphonium salts – preparation and applications in organic synthesis

• Anna Kuźnik,
• Roman Mazurkiewicz and
• Beata Fryczkowska

Beilstein J. Org. Chem. 2017, 13, 2710–2738, doi:10.3762/bjoc.13.269

• (104) led to the formation of 1,3-indanedione derivatives 105 in yields of 63–70% (Scheme 59) [72]. Nucleophilic displacement of the triphenylphosphonium group in α,β-di(alkoxycarbonyl)vinylphosphonium salts: Coumarins are an important class of natural compounds [73]. Yavari et al. developed a method

• nucleophilic displacement of the triphenylphosphonium group in intermediate α,β-di(alkoxycarbonyl)vinylphosphonium salts. Synthesis of 6-formylcoumarin derivatives and their application in the synthesis of dyads. Synthesis of di- and tricyclic coumarin derivatives in the reaction of pyrocatechol with two

• vinylphosphonium salt molecules. Synthesis of mono-, di-, and tricyclic derivatives in the reaction of pyrogallol with one or two vinylphosphonium salt molecules. Synthesis of 1,4-benzoxazine derivative by nucleophilic displacement of the triphenylphosphonium group in intermediate α,β-di(methoxycarbonyl

Influence of the milling parameters on the nucleophilic substitution reaction of activated β-cyclodextrins

• László Jicsinszky,
• Kata Tuza,
• Giancarlo Cravotto,
• Andrea Porcheddu,
• Francesco Delogu and
• Evelina Colacino

Beilstein J. Org. Chem. 2017, 13, 1893–1899, doi:10.3762/bjoc.13.184

• intermediate for the preparation of 6I-S-monodeoxy-6I-monothio-β-CD [26]. Having selected the 6I-O-monotosyl-β-CD (Ts-β-CD) as the benchmark, the nucleophilic displacement of the tosylate group in the presence of azido or thiourea (TU) nucleophiles was chosen for the study under different milling conditions

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• under ball-milling conditions by using two equivalents of sodium hydroxide. Deprotonation of the N–H group increased the nucleophilicity of the nitrogen atoms, enabling the nucleophilic displacement reaction with two equivalents of 4-bromobenzyl bromide to yield di(4-bromobenzyl)urea 34 in 41%, after a

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• , enantiospecific nucleophilic displacement reactions [66][67]. α-Fluorinations The stereoselective electrophilic α-fluorination of carbonyl compounds became a thoroughly investigated field over the course of the last 15 years [68][69][70][71][72]. A variety of different catalytic approaches, either relying on the

• ][101]. Several strategies to access these valuable motives in an enantioenriched fashion have been reported in the past. One option would be to use already α-functionalized (i.e., halogenated) carbonyl compounds and carry out functional group interconversions, like, e.g., stereospecific nucleophilic

• displacement reactions [87]. Another powerful strategy would be the use of prochiral α-halocarbonyl compounds for asymmetric Darzens-type reactions to obtain chiral α,β-epoxycarbonyl compounds, which has been rather successfully demonstrated under chiral phase-transfer catalysis in the past [18][102][103][104