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

• -dioxaoctane (21) and 1,13-diamino-4,7,10-trioxatridecane (22) in DMSO at 70 °C for 30 min to form amino-conjugates 23 and 24 in 71 and 84% yield, respectively, containing ethylene glycol linkers with terminal primary amino groups (Scheme 6). The presence of ethylene glycol residues in bioactive molecules is

• linkers capable to connect these porphyrins with biomolecules, thus improving their biomedical characteristics and theraputic efficacy for PDT and BNCT due to the combination of different substituents within porphyrin framework. Amide coupling of A3B-type carboranylporphyrin containing an amino

Possible bi-stable structures of pyrenebutanoic acid-linked protein molecules adsorbed on graphene: theoretical study

• Yasuhiro Oishi,
• Motoharu Kitatani and
• Koichi Kusakabe

Beilstein J. Org. Chem. 2024, 20, 570–577, doi:10.3762/bjoc.20.49

• ) linkers on graphene. The activation barrier between two bi-stable conformations exhibited by PASE is confirmed to be based on the steric hindrance effect between a hydrogen on the pyrene group and a hydrogen on the alkyl group of this molecule. Even after the protein is supplemented, this steric hindrance

• the steric hindrance effect between two hydrogen atoms in the molecule. A discussion on how the activation barrier between possible conformations of a protein immobilized on graphene by linkers appears is also provided. We consider the adsorption of the linker molecule forming a bond with a protein

• , the magnitude of the activation barrier is expected to be close to that in PASE. This is expected to be the case since a protein weakly bound to the carbon graphitic network can be supplemented onto graphene only by linkers as PASE, which has often been observed experimentally [1]. This type of

Elucidating the glycan-binding specificity and structure of Cucumis melo agglutinin, a new R-type lectin

• Jon Lundstrøm,
• Emilie Gillon,
• Valérie Chazalet,
• Nicole Kerekes,
• Antonio Di Maio,
• Ten Feizi,
• Yan Liu,
• Annabelle Varrot and
• Daniel Bojar

Beilstein J. Org. Chem. 2024, 20, 306–320, doi:10.3762/bjoc.20.31

• a variety of linkers with which these molecules are immobilized. In general, we observed two binding preferences that were strongly enriched among bound sequences, namely glycans containing Fucα1-2Gal epitopes and glycans containing terminal GalNAc residues (Figure 2c). Amongst the bound sequences

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• pyrrole unit to one of the dithiole rings of an IF-TTF, allowing for dimerization of extended TTFs via the nitrogen atom by different linkers [14]. Donor–acceptor chromophores can be obtained by replacing one of the dithiafulvene (DTF) rings of the IF-TTF by an electron acceptor. Cyclic and acyclic

Active-metal template clipping synthesis of novel [2]rotaxanes

• Cătălin C. Anghel,
• Teodor A. Cucuiet,
• Niculina D. Hădade and
• Ion Grosu

Beilstein J. Org. Chem. 2023, 19, 1776–1784, doi:10.3762/bjoc.19.130

• ). Thanks to the symmetry of the axle and non-symmetry of the macrocycle the signals of the components could be easily distinguished by integrals. The aliphatic region is crowded with triplets corresponding to the ethyleneglycole and pentyl linkers. However, the difference in symmetry allowed the

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• linked through alkyl ether linkers, creating a crown ether-like core around the periphery of the calix[4]arene macrocycle (Scheme 3) [104]. The conformationally cone-locked receptor 7 showed the binding of monohydrated fluoride within the core. The F− anion was encapsulated within the central cavity

• accordion porphyrins with various linkers [54][125]. Their formation typically relied on a template synthesis approach [126][127]. The first reported accordion porphyrin was synthesised as a binucleated lead(II) complex 13 (Scheme 4) [52]. The reaction of diformyldipyrromethane 12, lead(II) thiocyanate, and

• 1,3-diaminopropane yielded 13 selectively. Later, Bowman-James and co-workers introduced a series of binucleated accordion porphyrins differing in the linkers connecting two parts of the dimeric macrocycle exploiting the barium(II)-templated reactions [53]. The coordination chemistry of accordion

Linker, loading, and reaction scale influence automated glycan assembly

• Marlene C. S. Dal Colle,
• Manuel G. Ricardo,
• Nives Hribernik,
• José Danglad-Flores,
• Peter H. Seeberger and
• Martina Delbianco

Beilstein J. Org. Chem. 2023, 19, 1015–1020, doi:10.3762/bjoc.19.77

• mostly performed on cross-linked polystyrene resins equipped with photocleavable linkers [3], offering orthogonality to all the synthetic steps of the assembly, while selectively releasing the glycan at the end of the synthesis. In recent years, the implementation of new synthetic strategies [4][5][6][7

• scale [19], and linkers [20][21] affect the overall yield of solid phase peptide synthesis (SPPS). In the past decades, several supports and linkers have been developed and commercialized for SPPS, enabling a wide range of applications. Solid supports are available with different linker loadings, with

• productivity of AGA. Results and Discussion We selected three glycan sequences as models to analyze the effect of different parameters on the AGA outcome. Each sequence was prepared on four batches of Merrifield resin functionalized with two photolabile linkers (L1 [22] vs L2 [3]), at two linker loadings (low

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• struts and the photoresponsive linkers. The use of ditopic interlocked building blocks, such as that employed to form mainly a cyclic hetero[4]pseudorotaxane from a self-complementary [2]rotaxane [73], is also envisioned as a strategy that will be employed in the future to dynamically change the

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• this [7]helicene family by introducing different linkers such as nitrogen, sulfur, sulfone, ketone, methylene, and derivatives of ketone [44]. Due to the varied nature of the different linkers, the photophysical and semiconductor properties can be effectively tuned. Feng and co-workers reported a

• reported a new family of chiral NGs, which constituted by two orthogonal dibenzo[fg,ij]phenanthro-[9,10,1,2,3-pqrst]pentaphene (DBPP) units covalently connected through tetrafluorophenylene (61) [49] or octafluoro-9,10-anthracenylene (65) [50] linkers. The synthesis started with a double Pd-catalyzed

• nanographenes 96 and 100 using helicene or oxa-helicene as the linkers, respectively [56]. The first π-extension started from the borylated penta-tert-butyl HBC 92. The chemical selective Suzuki−Miyaura cross-coupling reaction between 92 and 93 followed by Scholl oxidation produced compound 94 in an overall 50

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• ) [77][78]. The allyl moiety in 144 allows for facile further functionalization. Amidation of the dihydrodibenzo[b,f]azepine (2a) derivatives with acyl halides 145 allowed for the introduction of variable length amide linkers by Kastrinsky et al. [3] (Scheme 33B). An industrial synthesis of opipramol (5

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

• Semyon V. Tsybulin,
• Ekaterina A. Filatova,
• Alexander F. Pozharskii,
• Valery A. Ozeryanskii and
• Anna V. Gulevskaya

Beilstein J. Org. Chem. 2023, 19, 674–686, doi:10.3762/bjoc.19.49

• , including naphthalene cores, butadiyne and acetylene linkers. The main structural parameters of diynes 5 that characterize the degree of this distortion are presented in Table 2, where ϕ1 is the angle between the planes of the benzene ring and the neighboring naphthalene system, ϕ2 is the angle between the

• characterized by the least distortion of the DMAN fragments in the series (twisting Θ = 9.45 and 12.83°, torsions φA = 20.9° and φB = 8.4°, bond angle deviations in both butadiyne and acetylene linkers do not exceed 6°). In the crystal packing of 5d (see Supporting Information File 1, Figures S64 and S65), the

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

• -triazole-ruthenium(II) conjugates 112a,b and 116a,b in 18–20% yield. Their photophysical and electrochemical studies revealed that the orbital energies depend on the ligands/linker, connecting pattern of linkers, and the presence of Zn metal ions in the porphyrin core. Ligand exchange studies also

• 126, it was used to form water-soluble porphyrin nanospheres by self-inclusion complex formation in water. Tritriazole-bridged porphyrin system This section contains the synthesis of porphyrin conjugates having three 1,2,3-triazole groups as linkers. In 2012, Beletskaya and co-workers [55] described

• % yield using Cu(MeCN)4PF6 and triethylamine in anhydrous DMF. This ‘capped’ porphyrin was designed so that the rigid triazole linkers prevent the capping group from collapsing onto the porphyrin. Gilday et al. [60] also synthesized porphyrin 142 and studied its anion-binding properties and found that it

A study of the DIBAL-promoted selective debenzylation of α-cyclodextrin protected with two different benzyl groups

• Naser-Abdul Yousefi,
• Morten L. Zimmermann and
• Mikael Bols

Beilstein J. Org. Chem. 2022, 18, 1553–1559, doi:10.3762/bjoc.18.165

• linkers, lids or catalytic groups can be installed which is no simple task due to the many similar functionalities in 1 [5][6][7]. A very useful way to access the hydroxy groups in a selective manner is the perbenzylation of 1 and the subsequent selective debenzylation of 2 using DIBAL [8][9][10]. This

An alternative C–P cross-coupling route for the synthesis of novel V-shaped aryldiphosphonic acids

• Stephen J. I. Shearan,
• Enrico Andreoli and
• Marco Taddei

Beilstein J. Org. Chem. 2022, 18, 1518–1523, doi:10.3762/bjoc.18.160

• Abstract The synthesis of phosphonate esters is a topic of interest for various fields, including the preparation of phosphonic acids to be employed as organic linkers for the construction of metal phosphonate materials. We report an alternative method that requires no solvent and involves a different

• . Phosphonates can also be employed as organic linkers in combination with metal ions to afford coordination polymers and metal-organic frameworks (MOFs), or more aptly, metal phosphonate frameworks [19][20]. One of the main challenges in the synthesis of metal phosphonates is that the linkers are rarely

• organic linkers for the synthesis of open framework metal phosphonate materials. The proposed protocol does not require a solvent, while featuring reaction times and yields comparable, if not better, to those of most procedures commonly employed in the literature. Results and Discussion The goal of this

Naphthalimide-phenothiazine dyads: effect of conformational flexibility and matching of the energy of the charge-transfer state and the localized triplet excited state on the thermally activated delayed fluorescence

• Kaiyue Ye,
• Liyuan Cao,
• Davita M. E. van Raamsdonk,
• Zhijia Wang,
• Jianzhang Zhao,
• Daniel Escudero and
• Denis Jacquemin

Beilstein J. Org. Chem. 2022, 18, 1435–1453, doi:10.3762/bjoc.18.149

• above, various approaches (different connection, linkers, oxidation of the PTZ, and addition of methyl groups) have been used to tune the relative energies of the key states and the geometry. Scheme 1 summarizes the synthetic routes used to obtain the various compounds and shows the molecular structures

Mechanochemical bottom-up synthesis of phosphorus-linked, heptazine-based carbon nitrides using sodium phosphide

• Blaine G. Fiss,
• Georgia Douglas,
• Michael Ferguson,
• Jorge Becerra,
• Jesus Valdez,
• Trong-On Do,
• Tomislav Friščić and
• Audrey Moores

Beilstein J. Org. Chem. 2022, 18, 1203–1209, doi:10.3762/bjoc.18.125

• constitutes the building block of g-CN, as opposed to in a linking position. Computational studies by Hartley and Martsinovich have investigated the influence of various linkers, including phosphorus atoms, on both the structure and optical behavior of heptazine-based graphitic carbon nitrides [3]. Yet

• , examples of carbon nitride materials linked together via phosphorus atoms are limited, likely due to challenges in controlling the insertion of phosphorus atoms as linkers under high energy conditions. Mechanochemistry [9][10][11][12] has proven to be effective for the synthesis of a variety of polymers

• establish phosphorus atoms are linkers between heptazine units, X-ray photoelectron spectroscopy (XPS) was used to probe the surface. In g-h-PCN, XPS scans focused on carbon 1s showed three major peaks at 284.7, 286.4, and 288.6 eV, corresponding to C=N, C–OH and C=O signals, respectively (Figure 2a), as

Post-synthesis from Lewis acid–base interaction: an alternative way to generate light and harvest triplet excitons

• Hengjia Liu and
• Guohua Xie

Beilstein J. Org. Chem. 2022, 18, 825–836, doi:10.3762/bjoc.18.83

• highly depends on the molecular design and structures, including linkers, donor and acceptor units, which requires complex and time-consuming molecular synthesis and optimization [21][22][23]. In contrast, the introduction of specific Lewis acid–base pairs in existing molecules can be utilized to achieve

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• advantages of utilizing self-assembly to construct discrete nanocages with predetermined geometry and function is the use of a one-pot reaction employing complementary organic linkers with inorganic metal ions. Although the one-pot synthesis of homoleptic metallacages has been thoroughly investigated over

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• -alkylene-linkers, the diastereoselectivity decreases with increasing linker length (79/33/12% de for C3/C6/C12-linkers, respectively). This is in line with an expected localization of the macrocycle around the ester functionality due to weak [C–H···O] interactions from the COOCH2 group to the macrocycle

• ) and in the substitution pattern of the macrocycle (R = H or iPr in the 3,5-positions of the phenylene linkers, for 56 or 57; see Figure 14). These heterobifunctional chiral catalysts were studied for the asymmetric Michael addition of malonic acid diethyl ester (59) to cinnamaldehydes 58. While the

Stepwise PEG synthesis featuring deprotection and coupling in one pot

• Logan Mikesell,
• Dhananjani N. A. M. Eriyagama,
• Yipeng Yin,
• Bao-Yuan Lu and
• Shiyue Fang

Beilstein J. Org. Chem. 2021, 17, 2976–2982, doi:10.3762/bjoc.17.207

• obtained. However, for many other applications, which include as linkers in organic synthesis and bioconjugation [8], as ingredients in nanomedicines to stabilize nanoparticles and to assist nanoparticle cell entry [9][10][11], and as PEGylation agents to stabilize drugs based on biologic molecules such as

• protecting groups would be preferred. Such routes can double the length of the PEG in three easy steps and the PEG product is asymmetric. It is noted that the use of base-labile protecting groups or linkers in organic synthesis involving carrying out reactions under less basic reactions and removing the

• protecting group or cleaving the linker under more basic conditions is not common. In contrast, the use of acid-labile protecting groups or linkers involving carrying out reactions under less acidic conditions and removing the protecting group or cleaving the linker under more acidic conditions is more

Total synthesis of the O-antigen repeating unit of Providencia stuartii O49 serotype through linear and one-pot assemblies

• Tanmoy Halder and
• Somnath Yadav

Beilstein J. Org. Chem. 2021, 17, 2915–2921, doi:10.3762/bjoc.17.199

• for further conjugation to other moieties towards the synthesis of vaccine conjugates by removal of the anomeric PMP group. This has been previously demonstrated by removal of the anomeric PMP group, conversion to a glycosidic donor, and further conjugation to either linkers or amino acids by several

Constrained thermoresponsive polymers – new insights into fundamentals and applications

• Patricia Flemming,
• Alexander S. Münch,
• Andreas Fery and
• Petra Uhlmann

Beilstein J. Org. Chem. 2021, 17, 2123–2163, doi:10.3762/bjoc.17.138

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• , and polymeric isoindigos as agents for photoacoustic and photothermal cancer therapy. Processing conditions and additive influence on OSC performance based on monoisoindigos 9a–c. Structures of linkers in bisisoindigos 14 and 15 and the performance of OSCs based on these. Photovoltaic properties of

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