Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• investigated. When o-terphenyl (10.1) was milled (30 Hz, PTFE balls) and irradiated (λ = 270 nm) in the presence of silica gel (bulking agent), I2 (1 equiv) as an oxidant, and K2CO3 (1 equiv) as a base in the presence of toluene, the expected product 10.2 was obtained in 81% yield after isolation upon 181 h of

Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• Å (5%) in the acid–acid distance (rCC) is observed along with an increase in twist by 2° (i.e. ≈ −0.1 Å/°) [39][41]. This twist can in turn be controlled by the dihedral angle of the central component of the terphenyl group (Figure 9A) – for anthracene cage 4e, an increased dihedral angle due to a

C–C Coupling in sterically demanding porphyrin environments

• Liam Cribbin,
• Brendan Twamley,
• Nicolae Buga,
• John E. O’ Brien,
• Raphael Bühler,
• Roland A. Fischer and
• Mathias O. Senge

Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234

• larger π-systems, e.g., 15, K3PO4 was required to achieve the tetra-coupled product. This trend is consistent in reactivity observed with porphyrins 12 and 13. Similarly, no terphenyl product was formed in the coupling reaction between 12 and 17 (Table 2, entry 6) when using Cs2CO3. Similar to the

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• ) demonstrates the synthetic utility of the developed method. Keywords: aniline; benzannulation; condensation; 1,3-diketone; Hammett constants; terphenyl; Introduction The aniline moiety is omnipresent in the synthetic chemistry with applications ranging from building blocks to catalysis [1][2][3][4]. Among

• (Figure 1). On the other hand, 3,5-diarylanilines can be regarded as meta-terphenyls which are of great interest for material and coordination chemistry [5][6][7][8][9][10][11][12][13][14][15][16]. Moreover, compounds with diverse bioactivities and natural products contain the meta-terphenyl moiety as a

Rhodium-catalyzed homo-coupling reaction of aryl Grignard reagents and its application for the synthesis of an integrin inhibitor

• Kazuyuki Sato,
• Satoki Teranishi,
• Atsushi Sakaue,
• Yukiko Karuo,
• Atsushi Tarui,
• Kentaro Kawai,
• Hiroyuki Takeda,
• Tatsuo Kinashi and
• Masaaki Omote

Beilstein J. Org. Chem. 2024, 20, 1341–1347, doi:10.3762/bjoc.20.118

• amount of 3,3''-difluoro-1,1':3',1''-terphenyl (6h) as side product, that might derive from an SNAr reaction of 3h with the Grignard reagent of 5h. Moreover, bromoxylenes 5m–o also gave the corresponding products 3m–o, respectively, although the position of substituents affected the yields. On the other

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• ]hexanes have been suggested as another BCH-based scaffold suggested for isosteric replacement of meta-benzenes [14]. Exit vector analysis of 1,4-BCH 98 and m-terphenyl (95) has been reported by Walker and co-workers (Figure 17) [34]. It shows that while the substituent distances d are remarkably similar

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• their phenanthrenyl and terphenyl counterparts exhibited noteworthy emission behavior in solid form and in solutions (Figure 6). For instance, the fluorenyl derivatives 68 and 69, phenanthrenyl derivative 70, and terphenyl derivative 71 exhibited fluorescence characterized by emission peaks at 596, 595

Isolation and biosynthesis of daturamycins from Streptomyces sp. KIB-H1544

• Yin Chen,
• Jinqiu Ren,
• Ruimin Yang,
• Jie Li,
• Sheng-Xiong Huang and
• Yijun Yan

Beilstein J. Org. Chem. 2022, 18, 1009–1016, doi:10.3762/bjoc.18.101

• Chinese Academy of Sciences, Beijing 100049, China 10.3762/bjoc.18.101 Abstract Two novel diarylcyclopentenones daturamycin A and B (1 and 2), and one new p-terphenyl daturamycin C (3), along with three known congeners (4–6), were isolated from a rhizosphere soil-derived Streptomyces sp. KIB-H1544. The

• daturamycins was identified through gene knockout and biochemical characterization experiments and the biosynthetic pathway of daturamycins was proposed. Keywords: biosynthesis; diarylcyclopentenone; polyporic acid synthetase; p-terphenyl; Streptomyces; Introduction Natural products containing a terphenyl

• skeleton exhibit a large number of structural diversity due to the differences of the center ring and the connection among rings. Structurally, most natural terphenyls are p-terphenyl derivatives consisting of a C-18 tricyclic or polycyclic C-18 aromatic skeleton. Diarylcyclopentenones, which possess a

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• aromatic ketones (Scheme 27) [61]. The authors coupled acetophenone derivatives 116 and 1,4-benzenediboronates 117 at a 2:1 ratio, to obtain p-terphenyl derivatives 118. In the second step, the conversion of the acetyl group of compounds 118 to an ethynyl group afforded diethynylterphenyls 119. In the last

• double cyclization and concluded that the reaction strongly depended on the position of the ethynyl groups in the terphenyl compounds. Terphenyls 125 were the most appropriate to prepare dibenzo[a,h]anthracenes in good yield (49–92%). AuCl was a notable catalyst because it maintained high cyclization

• 129a and 129b in two steps. First, they subjected dibromides 127 to a double Suzuki coupling with 4-alkylphenylboronic acids, to obtain the terphenyl derivatives 128. Then, the authors converted compounds 128, in moderate yield (54–55%), to the corresponding 6,8-diiododibenzo[a,j]anthracenes 129a and

Helicene synthesis by Brønsted acid-catalyzed cycloaromatization in HFIP [(CF₃)₂CHOH]

• Takeshi Fujita,
• Noriaki Shoji,
• Nao Yoshikawa and
• Junji Ichikawa

Beilstein J. Org. Chem. 2021, 17, 396–403, doi:10.3762/bjoc.17.35

• -catalyzed cycloaromatization (Scheme 3, route a and Scheme 4a). Treatment of 1,2-dibromobenzene (2a) with 3 in the presence of a palladium catalyst with SPhos afforded o-terphenyl derivative 4a bearing two acetal groups in 96% yield (Scheme 4a). The obtained bisacetal 4a successfully underwent

• otherwise noted, materials were obtained from commercial sources and used directly without further purification. 2,2''-Bis[(1,3-dioxolan-2-yl)methyl]-1,1':2',1''-terphenyl (4a) A dioxane (6.6 mL) and H2O (3.4 mL) solution of 1,2-dibromobenzene (2a, 471 mg, 2.00 mmol), boronate ester 3 (1.27 g, 4.39 mmol

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• acids in the presence of Pd(PPh3)4 and K2CO3 in THF/water to furnish the required hexaarylated sumanenes in 20–85% yields (Scheme 23). In the same year, the groups of Hisaki, Sato and Sakurai have reported a hydrogen-bonded 2D sumanene buckybowl framework having 4,4’-dicarboxy-o-terphenyl groups in the

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

• Md. Shafiqur Rahman and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

• , FeCl3, Cu(OTf)2, and AlCl3 failed to promote the cyclization of 7a to 8a. The PIFA/BF3·OEt2 system also promoted the Scholl reaction of terphenyl 7b bearing a methylenedioxy moiety with a comparable efficiency to afford 8b in 56% yield. Compound 8c, a naphthylene-linked analogue of 8a, also underwent

Synthesis and optoelectronic properties of benzoquinone-based donor–acceptor compounds

• Daniel R. Sutherland,
• Nidhi Sharma,
• Georgina M. Rosair,
• Ifor D. W. Samuel,
• Ai-Lan Lee and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2019, 15, 2914–2921, doi:10.3762/bjoc.15.285

• for C36H22N2O2, 515.1760; found, 515.1760. 4,4''-Bis(diphenylamino)[1,1':4',1''-terphenyl]-2',5'-dione (5): To a Schlenk tube equipped with a magnetic stirring bar were added 2,5-dibromocyclohexa-2,5-diene-1,4-dione (251 mg, 0.94 mmol, 1 equiv), 4-(diphenylamino)phenylboronic acid (809 mg, 2.80 mmol

Acid-catalyzed rearrangements in arenes: interconversions in the quaterphenyl series

• Sarah L. Skraba-Joiner,
• Carter J. Holt and
• Richard P. Johnson

Beilstein J. Org. Chem. 2019, 15, 2655–2663, doi:10.3762/bjoc.15.258

• [20][21]. One classic example of arenium ion chemistry is the interconversion of terphenyl isomers 1–3 (Scheme 1). This rearrangement was first reported by Allen and Pingert in 1942 [22] and then independently rediscovered by Olah and Meyer twenty years later [23]. Interconversion of isomers 1–3 is

• protonation is the essential step in arenium ion rearrangements. Our interest in this field arose from an accidental rediscovery of rearrangements in the terphenyl series (1–3; Scheme 1), by heating 1 with AlCl3 – a reaction independently discovered twice before [22][23]! We confirmed earlier observations of

• facile acid-catalyzed interconversion, as well as the fact that m-terphenyl (2) is favored at equilibrium (observed ratio 1:2:3 is <1:69:31) and used theory to explain this product selectivity [25]. This preference is consistent with formation of the most stable arenium ion intermediate, as shown by DFT

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• written information is then read out by a non-perturbing lower voltage. It turned out that the terphenyl spacer which is implemented into the rotaxane axle is crucial to increase the half-life of the metastable switching state. However, a disadvantage of this particular device was a high fraction of

A pyridinium/anilinium [2]catenane that operates as an acid–base driven optical switch

• Sarah J. Vella and
• Stephen J. Loeb

Beilstein J. Org. Chem. 2018, 14, 1908–1916, doi:10.3762/bjoc.14.165

• (pyridinium)ethane recognition sites linked by terphenyl spacer groups [17] (Figure 2). It was thus of interest to design and build these two different recognition sites (benzylanilinium and bis(pyridinium)ethane) into an analogous circumrotational [2]catenane molecular switch to compare to the linear [2

• (Figure 2) was synthesized using a one-step, self-assembly procedure from two bis(pyridinium)ethane axles, two terphenyl spacers and two DB24C8 crown ethers, a [2]catenane with different recognition sites requires a stepwise approach involving the incorporation of each recognition site independently

• . Overall, the synthesis of [2]catenane [8DB24C8]6+ required multiple steps and is outlined in Scheme 1. Two literature preparations were used to construct each of the known compounds, terphenyl linker 6 [18] and bis(pyridinium)ethane axle [5][OTf]2 [19][20], while the new benzylaniline axle 4 was prepared

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

Elongated and substituted triazine-based tricarboxylic acid linkers for MOFs

• Arne Klinkebiel,
• Ole Beyer,
• Barbara Malawko and
• Ulrich Lüning

Beilstein J. Org. Chem. 2016, 12, 2267–2273, doi:10.3762/bjoc.12.219

• proper analyses and future use in solvothermal syntheses of MOFs. Tribromotriazines 3 are not only good starting materials for the syntheses of biphenyl-substituted triazine linkers 16 and 17. Also longer terphenyl-substituted linkers can be obtained if the same approach is chosen but a biphenylboronic

• acid derivative such as boronate 18 [12] is used instead of the phenyl compound 15. As in the case of the biphenyl derivatives 16 and 17, the nitro and the methoxy-substituted triazines 3b and 3c were used to obtain the terphenyl-based nitro and methoxy-substituted triesters 19b and 19c (Figure 8). But

• also the non-substituted precursor 3a was coupled leading to the unsubstituted parent compound 19a, a triester which has not been described yet. Direct hydrolyses of triesters 19a and 19b gave the carboxylic acids 20a and 20b. Finally, a hydroxy-functionalized terphenyl-based linker was synthesized

Syntheses of dibenzo[d,d']benzo[2,1-b:3,4-b']difuran derivatives and their application to organic field-effect transistors

• Minh Anh Truong and
• Koji Nakano

Beilstein J. Org. Chem. 2016, 12, 805–812, doi:10.3762/bjoc.12.79

• -isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (iPrO-Bpin) gave boronate ester 7 in 57% yield. Then, terphenyl 9 was synthesized via palladium-catalyzed Suzuki–Miyaura cross coupling of boronate ester 7 with 2,3-difluoro-1,4-diiodobenzene (96% yield) and subsequent demethylation (95% yield). Finally, the

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• corresponding dibromide followed by formylation (Scheme 13). In 2006, Rajkumar and co-workers [103] have published the synthesis of stilbenophane 85 via McMurry coupling as a key step (Scheme 14). Terphenyl derivative 82 was subjected to benzylic bromination in the presence of NBS to generate compound 83. Later

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing

• Bradley D. Rose,
• Peter J. Santa Maria,
• Aaron G. Fix,
• Chris L. Vonnegut,
• Lev N. Zakharov,
• Sean R. Parkin and
• Michael M. Haley

Beilstein J. Org. Chem. 2014, 10, 2122–2130, doi:10.3762/bjoc.10.219

• Kitamura gave tetrahalide 12 in good yield on >10 g scale [25]. Suzuki cross-coupling with 12 furnished p-terphenyl 14, followed by oxidation of the methyl groups to produce diacid 15. Intramolecular Friedel–Crafts acylation then afforded 5,11-dibromo-IF-dione 11. The yields for the Sonogashira cross

Synthesis of rigid p-terphenyl-linked carbohydrate mimetics

• Maja Kandziora and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 1749–1758, doi:10.3762/bjoc.10.182

• . Unnatural divalent rigid p-terphenyl-linked C-aryl glycosides with 2.0 nm dimension are available using Suzuki cross-couplings. The key compound, a p-bromophenyl-substituted 1,2-oxazine, was prepared by a stereoselective [3 + 3]-cyclization of a D-isoascorbic acid-derived (Z)-nitrone and lithiated TMSE

• -couplings to form biphenyl aminopyran or p-terphenyl-linked dimers. Hydrogenolysis afforded new unnatural aminosugar mimetics. Zinc in the presence of acid or samarium diiodide were examined for the N–O bond cleavage in order to obtain the rigid p-terphenyl-linked C-glycosyl dimers. Keywords: carbohydrate

• synthesis of divalent compounds 1 with p-terphenyl spacers and of β-D-2-aminotalose- or β-D-2-aminoidose-configured carbohydrate mimetics 2 (Scheme 1). These novel carbohydrate mimetics represent unique structures, combining the features of C-aryl-glycosides and aminosugars. The p-bromophenyl-substituted

Rapid pseudo five-component synthesis of intensively blue luminescent 2,5-di(hetero)arylfurans via a Sonogashira–Glaser cyclization sequence

• Fabian Klukas,
• Alexander Grunwald,
• Franziska Menschel and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 672–679, doi:10.3762/bjoc.10.60

• recorded in dichloromethane and the fluorescence quantum yields Φf were determined with coumarin 1 or p-terphenyl as references (Table 2). The most furans display intense, broad absorption bands between 321 and 358 nm with molar extinction coefficients between 21000 to 35000 L/mol cm−1. In addition

• (22000). Fluorescence (CH2Cl2): λmax: 358 nm. Stokes shift Δ = 3800 cm−1. Quantum yield: Φf = 83% (Ref.: p-terphenyl (Φf = 93% in cyclohexane)). Cyclic voltammetry (CH2Cl2): E1/20/+1 = 1.25 V. Compounds 2d (solid and THF solution) and 2n (solid and THF solution) (from left to right) under daylight (top

Parallel solid-phase synthesis of diaryltriazoles

• Matthias Wrobel,
• Jeffrey Aubé and
• Burkhard König

Beilstein J. Org. Chem. 2012, 8, 1027–1036, doi:10.3762/bjoc.8.115

• a rapid synthesis of the target compounds in a parallel fashion with in many cases good to excellent yields. Substituted diaryltriazoles resemble a molecular structure similar to established terphenyl-alpha-helix peptide mimics and have therefore the potential to act as selective inhibitors for

• is another successful strategy [11]. Horwell pioneered this type of peptidomimetics and showed that 1,6-disubstituted indanes can imitate the helix residues i and i+1 [12][13]. Hamilton reported a 3,2′,2″-substituted terphenyl scaffold with a spatial orientation that mimics the i, i+3 and i+7

• moieties on the surface of an α-helical peptide [14]. Inspired by the terphenyl-based α-helix mimetics 1, several related compounds containing three or more adjacent aryl rings (Scheme 1), such as 2, were reported [15]. However, the synthesis of substituted triaryl compounds can be tedious, and the

The interplay of configuration and conformation in helical perylenequinones: Insights from chirality induction in liquid crystals and calculations

• Elisa Frezza,
• Silvia Pieraccini,
• Stefania Mazzini,
• Alberta Ferrarini and
• Gian Piero Spada

Beilstein J. Org. Chem. 2012, 8, 155–163, doi:10.3762/bjoc.8.16

• (Merck) nematic solvent E7 (nematic–isotropic transition temperature TNI ~ 330 K) is composed of a eutectic mixture of cyanobiphenyl and terphenyl compounds [30]. DFT calculations Atomic coordinates and energy of the conformers of 1 and 2 were obtained by geometry optimization in vacuum, by using DFT at