Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• fluorophenylporphyrin substituents via the boron atom. At the same time the SNAr substitution reaction for the azido-substituted porphyrin 2 with mercaptocarborane 4 also afforded the amino-substituted porphyrin 5 in 32% yield (Scheme 2). During the reaction the reduction of the azide group under the action of

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview

• Dileep Kumar Singh

Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29

• (56) in piperidine as shown in Scheme 10. To prepare these conjugates, a porphyrin with a pentafluorophenyl ring (because of its strong electron-withdrawing ability) was chosen and used in the synthesis of azidoporphyrin 51 by replacing the para-fluoro atom with an azide group. Interestingly, the

Efficient synthesis of aziridinecyclooctanediol and 3-aminocyclooctanetriol

• Emine Salamci and
• Ayse Kilic Lafzi

Beilstein J. Org. Chem. 2022, 18, 1539–1543, doi:10.3762/bjoc.18.163

• )cyclooctane-1,2-diyl dimethanesulfonate. Reaction of the bis(benzyloxy)cyclooctane-1,2-diyl dimethanesulfonate with NaN3 gave 2-azido-3,8-bis(benzyloxy)cyclooctyl methanesulfonate. Reduction of the azide group and debenzylation to give an amine provided the new 3-aminocyclooctanetriol. Treatment of the 2

• group in compound 10 was converted to the corresponding alcohol 11 as the sole isomer via SN2 substitution by hydrolysis. In the azidolysis reaction of compound 8, we propose that because the azide group is bulkier than the water molecule, it could not substitute the second mesylate group, and therefore

Site-selective reactions mediated by molecular containers

• Rui Wang and
• Yang Yu

Beilstein J. Org. Chem. 2022, 18, 309–324, doi:10.3762/bjoc.18.35

• equivalents of PMe3 to the post-reaction mixture after 24 hours still did not induce further reduction of the residual azide group. However, control experiments gave just the diamine products. This work opened the protective ability of water-soluble cavitands and inspired many other following examples of

(Phenylamino)pyrimidine-1,2,3-triazole derivatives as analogs of imatinib: searching for novel compounds against chronic myeloid leukemia

• Luiz Claudio Ferreira Pimentel,
• Lucas Villas Boas Hoelz,
• Henayle Fernandes Canzian,
• Frederico Silva Castelo Branco,
• Andressa Paula de Oliveira,
• Vinicius Rangel Campos,
• Floriano Paes Silva Júnior,
• Rafael Ferreira Dantas,
• Jackson Antônio Lamounier Camargos Resende,
• Anna Claudia Cunha,
• Nubia Boechat and
• Mônica Macedo Bastos

Beilstein J. Org. Chem. 2021, 17, 2260–2269, doi:10.3762/bjoc.17.144

• obtained from the nucleophilic substitution reaction of intermediate 8 in 85% yield. The 1H and 13C NMR spectra of compounds 8 and 9 were similar, but in the IR spectrum of intermediate 9, it was possible to observe the characteristic stretching of the azide group at 2103 cm−1. The 1,3-dipolar

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• compounds in excellent yields and short reaction times (Scheme 21B and C). The robustness of the manganese-catalyzed photo-flow reaction was demonstrated by a gram-scale preparation of the key intermediate in the synthesis of the pharmaceutical compound dantrolene (60) in high yields (Scheme 21D). The azide

• group is another powerful organic function present for example in zidovudine, a worldwide known anti-HIV drug, but also in its derivatives (61 and 62) (Scheme 22A), which can present 10-times higher activities against HIV replication [143]. In 2020 the same group reported the use of a manganese catalyst

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98

• protection of 16 followed by introduction of an azide group in the C-2′ position of the molecule to afford nucleoside 22. The treatment of azide 22 with pyrrolidine in acetonitrile followed by hydrogenation afforded aminonucleoside 23, which was used as a key intermediate for the synthesis of the double

Synthesis of multiply fluorinated N-acetyl-D-glucosamine and D-galactosamine analogs via the corresponding deoxyfluorinated glucosazide and galactosazide phenyl thioglycosides

• Vojtěch Hamala,
• Lucie Červenková Šťastná,
• Martin Kurfiřt,
• Petra Cuřínová,
• Martin Dračínský and
• Jindřich Karban

Beilstein J. Org. Chem. 2021, 17, 1086–1095, doi:10.3762/bjoc.17.85

• configuration. Thioglycosides 22–31, 34 and 36 were then hydrolyzed into the corresponding hemiacetals 37–48 using treatment with NBS in acetone/water (Scheme 4). To obtain the target fluoro analogs, the hemiacetals 37–48 were debenzylated and their azide group converted to an acetamide. Although palladium

Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols

• Emine Salamci and
• Yunus Zozik

Beilstein J. Org. Chem. 2021, 17, 705–710, doi:10.3762/bjoc.17.59

• the corresponding cyclic sulfate via the formation of a cyclic sulfite in the presence of catalytic RuO4. The reaction of this cyclic sulfate with a nucleophilic azide followed by the reduction of the azide group provided the target, 3-aminocyclooctanetriol. The second key compound, bromotriol, was

• prepared by epoxidation of the cyclooctenediol with m-chloroperbenzoic acid followed by hydrolysis with HBr(g) in methanol. Treatment of bromotriol with NaN3 and the reduction of the azide group yielded the other desired 3-aminocyclooctanetriol. Hydrolysis of the epoxides with HCl(g) in methanol gave

• with a large coupling constant (J2,3 = 8.8 Hz) are trans to each other. The small coupling constant (J3,4 = 2.7 Hz) between H-3 and H-4 shows the cis relationship between those protons. The configuration of the azide group in 11 was also confirmed by the cross peak between the proton H-3 and the

Supramolecular polymerization of sulfated dendritic peptide amphiphiles into multivalent L-selectin binders

• David Straßburger,
• Svenja Herziger,
• Katharina Huth,
• Moritz Urschbach,
• Rainer Haag and
• Pol Besenius

Beilstein J. Org. Chem. 2021, 17, 97–104, doi:10.3762/bjoc.17.10

• I was purified by size exclusion chromatography. In order to synthesize the sulfated, functionalized supramolecular building block II, we made use of the selective heterofunctionalization of trimesic acid. By replacing one of the solubilizing dodeca(ethylene glycol) moieties with an azide group

Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

• Vladimir Ilkin,
• Vera Berseneva,
• Tetyana Beryozkina,
• Tatiana Glukhareva,
• Lidia Dianova,
• Wim Dehaen,
• Eugenia Seliverstova and
• Vasiliy Bakulev

Beilstein J. Org. Chem. 2020, 16, 2937–2947, doi:10.3762/bjoc.16.243

• -Aminothiazole-4-N-sulfonyl amidines In spite of the presence of a nucleophilic amino group capable to react with sulfonyl azide to form an azide group, the reaction of azides 2 occurred selectively to the thioamide group of compound 1m. Thus, similar to the reaction of 5-arylamino-1,2,3-triazole-4

• the azide group and the C=S moiety of the thioamide group (Scheme 7). The formation of nitrene-like products was excluded because of the high selectivity of the process, where only the thioamide group takes part, even with heterocyclic rings that contain other nucleophilic centers, and in one case, an

Optical detection of di- and triphosphate anions with mixed monolayer-protected gold nanoparticles containing zinc(II)–dipicolylamine complexes

• Lena Reinke,
• Julia Bartl,
• Marcus Koch and
• Stefan Kubik

Beilstein J. Org. Chem. 2020, 16, 2687–2700, doi:10.3762/bjoc.16.219

• synthesized in the racemic and the enantiomerically pure form. The racemate rac-1 was obtained in four steps from triethylene glycol monomethyl ether by tosylation, substitution of the tosyl by an azide group, and reduction to obtain the corresponding amine (Scheme 1). This amine was coupled to racemic lipoic

Synthesis and characterization of S,N-heterotetracenes

• Astrid Vogt,
• Florian Henne,
• Christoph Wetzel,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2020, 16, 2636–2644, doi:10.3762/bjoc.16.214

• step, an azide group was introduced to 10 by lithiation with n-BuLi followed by the reaction with tosyl azide giving azide 11 in an excellent yield of 92%. Thermally induced ring-closure under release of nitrogen and formation of a nitrene intermediate was achieved by refluxing azide 11 in

A chemoenzymatic synthesis of ceramide trafficking inhibitor HPA-12

• Seema V. Kanojia,
• Sucheta Chatterjee,
• Subrata Chattopadhyay and
• Dibakar Goswami

Beilstein J. Org. Chem. 2019, 15, 490–496, doi:10.3762/bjoc.15.42

• , the primary hydroxy function of 7a was benzoylated to get 8. Compound 8 was mesylated with methanesulfonyl chloride (MsCl)/Et3N and the product reacted with NaN3/DMF at 90 °C to obtain the azide 9 (Scheme 2). We first attempted to convert 9 to the target compound 2 by i) converting the azide group to

•  3). Hence, we decided to debenzylate compound 9 prior to its reduction to the amine and subsequent acylation. Towards this (Scheme 4), oxidative debenzylation of 9 using DDQ yielded 10 in 84% yield. Treatment of 10 with LiAlH4 led to the reduction of the azide group to amine along with

A switchable [2]rotaxane with two active alkenyl groups

• Xiu-Li Zheng,
• Rong-Rong Tao,
• Rui-Rui Gu,
• Wen-Zhi Wang and
• Da-Hui Qu

Beilstein J. Org. Chem. 2018, 14, 2074–2081, doi:10.3762/bjoc.14.181

• alcohol with saturated NH4PF6 solution to obtain compound 5. For another key intermediate 8, containing an amide site for stabilizing the DB24C8 macrocycle, a 1,2,3-tris(dodecyloxy) benzene group as a stopper and an azide group which is used for the reaction with other moieties, was prepared through the

Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

• Vladimir A. Burilov,
• Guzaliya A. Fatikhova,
• Mariya N. Dokuchaeva,
• Ramil I. Nugmanov,
• Diana A. Mironova,
• Pavel V. Dorovatovskii,
• Victor N. Khrustalev,
• Svetlana E. Solovieva and
• Igor S. Antipin

Beilstein J. Org. Chem. 2018, 14, 1980–1993, doi:10.3762/bjoc.14.173

• gave molecular ion peaks with expulsion of two (in the case of 4) or four (in the case of 8) N2 fragments due to the lability of the azide group upon laser desorption [39]. The spatial structure of the product 8a was established by X-ray crystallography and is presented in Figure 1 including the atomic

Atom-economical group-transfer reactions with hypervalent iodine compounds

• Andreas Boelke,
• Peter Finkbeiner and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108

• , azidobenziodoxolones 36b (ABX), could be utilized for atom-economical reactions. Gillaizeau and co-workers developed an iron-catalysed oxyazidation of enamides 45 using ABX derivatives 36b (Scheme 24) [58]. The reaction proceeds with complete regio- and stereoselectivity introducing the azide group in C2 and the ester

Recent progress in the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres

• Myriam Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2017, 13, 2637–2658, doi:10.3762/bjoc.13.262

• reacted easily in a SN2 reaction to give a more functionalized molecule. For example, treatment of the chlorinated monofluoroalkene with NaN3 provided the corresponding N3-containing monofluoroalkene. The azide group underwent a 1,3-dipolar cycloaddition to give a 1,2,3-triazole, which is also a peptide

Synthesis, effect of substituents on the regiochemistry and equilibrium studies of tetrazolo[1,5-a]pyrimidine/2-azidopyrimidines

• Elisandra Scapin,
• Paulo R. S. Salbego,
• Caroline R. Bender,
• Alexandre R. Meyer,
• Anderson B. Pagliari,
• Tainára Orlando,
• Geórgia C. Zimmer,
• Clarissa P. Frizzo,
• Helio G. Bonacorso,
• Nilo Zanatta and
• Marcos A. P. Martins

Beilstein J. Org. Chem. 2017, 13, 2396–2407, doi:10.3762/bjoc.13.237

• proportion of 80:20). On the other hand, the less polar solvent CDCl3 induces the formation of 2-azidopyrimidine 4d at a proportion of 10:90. Here, the ring is opened to form the azide group bonded in the pyrimidine ring. This result is in agreement with the literature data [20][21][22][24][25][26][27][32

An efficient synthesis of a C₁₂-higher sugar aminoalditol

• Łukasz Szyszka,
• Anna Osuch-Kwiatkowska,
• Mykhaylo A. Potopnyk and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2017, 13, 2146–2152, doi:10.3762/bjoc.13.213

• building blocks. The synthesis was realized by a regioselective introduction of the azide group and subsequent protection–deprotection transformations. The chemical reactivity of the aminoalditol was tested in the reductive amination reaction with a selectively protected sucrose monoaldehyde. Keywords

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• ether group on the primary OH group (1a and 1c) or xylose derived building block containing a propargyl group on the secondary OH group (1b). Further, a comparatively lower yield for the cycloaddition reaction (3c) was obtained when both building blocks used contain a secondary azide group (2b) and a

Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

• Atsushi Tamura,
• Asato Tonegawa,
• Yoshinori Arisaka and
• Nobuhiko Yui

Beilstein J. Org. Chem. 2016, 12, 2883–2892, doi:10.3762/bjoc.12.287

• an axle polymer and commercially available 4-substituted benzoic acids as capping reagents. The terminal 2-amino-3-phenylpropyl groups of PEG-Ph-NH2 block the dethreading of the α-CDs after capping with 4-substituted benzoic acids. By this method, two series of azide group-terminated polyrotaxanes

• functional PRXs and can be applied to the fabrication of PRX-based supramolecular biomaterials. Keywords: azide group; biomaterials; click chemistry; cyclodextrin; polyrotaxane; Introduction Polyrotaxanes (PRXs) are a class of interlocked polymers that consist of an inclusion complex of cyclodextrins (CDs

• drug delivery [31]. Herein, alkynyl group-bearing fluorescent molecules were modified at the terminal azide group of the PRXs, and intracellular fluorescence imaging of the PRXs was performed to verify whether the terminally modified fluorescent molecules could be used for fluorescence imaging. First

Catalytic Wittig and aza-Wittig reactions

• Zhiqi Lao and
• Patrick H. Toy

Beilstein J. Org. Chem. 2016, 12, 2577–2587, doi:10.3762/bjoc.12.253

• seems that the required isocyanate or azide group containing precursors are readily synthesized from simple starting materials. Conclusion While great advances have been reported regarding the development of catalytic Wittig and aza-Wittig reactions, it remains to be seen how widely these methods will

Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

• Svetlana V. Vasilyeva,
• Vyacheslav V. Filichev and
• Alexandre S. Boutorine

Beilstein J. Org. Chem. 2016, 12, 1348–1360, doi:10.3762/bjoc.12.128

• [10][11][34]. Several different bifunctional linkers were designed and synthesized (Figure 3). All of them contain, on one side, an alkyne or azide group for "click chemistry” and, on the other side, either an amino group for interaction with electrophiles (for example, activated terminal phosphates

• . The linker 4 is designed for functionalization of either commercial amino-modified oligonucleotides or amine-bearing polyamides. It contains an alkyne group for CuAAC and an activated ester for the acylation of amino groups. The linkers 5–7 of different lengths contain an azide group for CuAAC and a