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Search for "macrocyclic compounds" in Full Text gives 28 result(s) in Beilstein Journal of Organic Chemistry.
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
- the possible future directions. Keywords: crown ethers; porphyrinoids; self-assembly; sensors; supramolecular chemistry; Introduction Many areas of modern supramolecular chemistry, organic, inorganic, materials and coordination chemistry, are based upon macrocyclic compounds of specifically-designed
- structures and tailored functions [1][2][3]. The design of novel macrocyclic compounds has laid the ground for phenomenal developments constituting supramolecular chemistry as a branch of chemical sciences. These fundamental developments included the discovery of crown ethers by Pedersen [4], followed by the
- synthesis of three-dimensional cryptands by Lehn [5], and spherands by Cram [6]. Later on, various classes of macrocyclic compounds were designed, demonstrating remarkable features in areas spreading from simple coordination chemistry [7], through host–guest chemistry, sensing [8], biomedicine [9], and
Graphical Abstract
Figure 1: Porphyrin and crown ether.
Figure 2: Timeline demonstrating the contributions into the crown ether–porphyrin chemistry.
Figure 3: Tetra-crowned porphyrin 1 and dimer 2 formed upon K+ binding.
Figure 4: meso-Crowned 25-oxasmaragdyrins 3a–c and their boron(III) complexes (3a–c)-BF2.
Scheme 1: CsF ion-pair binding of 4. The molecular structure of 4-CsF is shown on the right [101].
Figure 5: CsF ion pair binding by 5. The molecular structure of 5-CsF is shown on the right [102].
Scheme 2: Ion-pair binding by 6. The molecular structure of (6-CsCl)2 is shown on the right [103].
Scheme 3: Hydrated fluoride binding by 7 [104].
Figure 6: β-Crowned porphyrin 8.
Figure 7: Crown ether-capped porphyrins 9.
Figure 8: The capped porphyrin 10 and complex [10-PQ](PF6)2.
Figure 9: The double-capped porphyrin 11.
Figure 10: Selected examples of iminoporphyrinoids [58,122].
Scheme 4: The synthesis of 13.
Scheme 5: Tripyrrane-based crown ether-embedding porphyrinoid 15.
Figure 11: Macrocycles 16–19 and their coordination compounds.
Scheme 6: The flexibility of 16-Co [66].
Figure 12: Hexagonal wheel composed of six 16-Co(III) monomers [66].
Scheme 7: The synthesis of 16-V [67].
Figure 13: The molecular structure of dimers [16-Mn]2 [67].
Scheme 8: Synthesis of crownphyrins 28–33. Compounds 23a/b and 29a/b were obtained from 4,7,10-trioxa-1,13-tr...
Figure 14: The molecular structures of 22a, 34a·(HCl)2, and 29b [69].
Figure 15: Molecular structures of 22a-Pb and (29b)2-Zn [69].
Scheme 9: Reactivity of 29a/b.
Scheme 10: Synthesis of 36 and 37 [131].
Scheme 11: Synthesis of 40–45.
Figure 16: Potential applications of porphyrin-crown ether hybrids.
Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions
- Waldemar Iwanek
Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109
- Waldemar Iwanek Bydgoszcz University of Science and Technology, Faculty of Chemical Technology and Engineering, Seminaryjna 3, 85-326 Bydgoszcz, Poland 10.3762/bjoc.19.109 Abstract Resorcin[4]arenes (R[4]A) are macrocyclic compounds with a cavity structure. Despite a relatively small cavity
- ; Introduction Resorcin[4]arenes are macrocyclic compounds with a cavity structure formed from resorcinol and aldehydes [1]. Of particular significance is their crown conformation, which stems from the presence of 8 hydroxy groups on the upper rim and a hydrophobic cavity [2]. This property plays an important
Graphical Abstract
Scheme 1: Scheme of the formation of R[4]A complexes with sec-amines in ethanol depending on the amine used.
Figure 1: 1H NMR spectra of the 1:1 complex of R[4]A with pyrrolidine in DMSO-d6 and CDCl3 solution. The inte...
Scheme 2: The procedure for finding the most energetically stable complex R[4]A with a sec-amine and calculat...
Figure 2: Theoretically calculated (PBE0-D4/def2-mTZVPP/CPCM) structures of the R[4]A:pyrrolidine complex in ...
Figure 3: Structures of complexes with 1:1 stoichiometry between R[4]A and sec-amines in CHCl3 and DMSO, calc...
Figure 4: Geometrically optimized (PBE0-D4/def2-mTZVPP/CPCM(DMSO) structures of complexes with 1:2 stoichiome...
Figure 5: pKa values of protons of hydroxy groups not involved in the formation of hydrogen bonds in the R[4]...
Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities
- Jorge de Lima Neto and
- Paulo Henrique Menezes
Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31
- for synthesis. In general, the synthesis of these macrocyclic compounds can be accomplished by using two distinct disconnections (Scheme 3): one concerns the formation of the macrocycle through macrolactonization reaction from the former seco-acid formed from the Ar–O–Ar coupling from the aryl donor
- or absence of certain functional groups in the structure of these compounds, such as a cis double bond or the position of a hydroxy or methoxy group play a crucial role in their biological activity as will be shown later in this review (Figure 1). Although there are reviews dealing with macrocyclic
- compounds available in the literature, there is none which focuses only on combretastatins D and their isomers. Therefore, this review is divided into three main parts: the first comprises the isolation of these compounds from natural sources. In the following part, the biosynthetic pathway and the total
Graphical Abstract
Figure 1: Structures of some members of the combretastatin D series, corniculatolides, and isocorniculatolide...
Scheme 1: Biosynthetic pathway proposed by Pettit and co-workers.
Scheme 2: Biosynthetic pathway towards corniculatolides or isocorniculatolides proposed by Ponnapalli and co-...
Scheme 3: Retrosynthetic approaches.
Scheme 4: Attempt of total synthesis of 2 by Boger and co-workers employing the Mitsunobu approach [27].
Scheme 5: Total synthesis of combretastatin D-2 (2) reported by Boger and co-workers employing an intramolecu...
Scheme 6: Formal synthesis of combretastatin D-2 (2) by Deshpande and co-workers using the Mitsunobu conditio...
Scheme 7: Total synthesis of combretastatin D-2 (2) by Rychnovsky and Hwang [36].
Scheme 8: Divergent synthesis of (±)-1 form combretastatin D-2 (2) by Rychnovsky and Hwang [36].
Scheme 9: Enantioselective synthesis of 1 by Rychnovsky and Hwang employing Jacobsen catalyst [41].
Scheme 10: Synthesis of fragment 57 by Couladouros and co-workers [43,45].
Scheme 11: Formal synthesis of compound 2 by Couladouros and co-workers [43,45].
Scheme 12: Synthesis of fragment 66 by Couladouros and co-workers [44,45].
Scheme 13: Synthesis of fragment 70 by Couladouros and co-workers [44,45].
Scheme 14: Synthesis of fragment 77 by Couladouros and co-workers [44,45].
Scheme 15: Synthesis of combretastatins 1 and 2 by Couladouros and co-workers [44,45].
Scheme 16: Formal synthesis of compound 2 by Gangakhedkar and co-workers [48].
Scheme 17: Synthesis of fragment 14 by Cousin and co-workers [50].
Scheme 18: Synthesis of fragment 91 by Cousin and co-workers [50].
Scheme 19: Formal synthesis of compound 2 by Cousin and co-workers [50].
Scheme 20: Synthesis of 2 diolide by Cousin and co-workers [50].
Scheme 21: Synthesis of combretastatin D-4 (4) by Nishiyama and co-workers [54].
Scheme 22: Synthesis of fragment 112 by Pettit and co-workers [55].
Scheme 23: Synthesis of fragment 114 by Pettit and co-workers [55].
Scheme 24: Attempt to the synthesis of compound 2 by Pettit and co-workers [55].
Scheme 25: Synthesis of combretastatin-D2 (2) starting from isovanilin (80) by Pettit and co-workers [55].
Scheme 26: Attempted synthesis of combretastatin-D2 (2) derivatives through an SNAr approach [55].
Scheme 27: Synthesis of combretastatin D-4 (4) by Pettit and co-workers [55].
Scheme 28: Synthesis of combretastatin D-2 (2) by Harras and co-workers [57].
Scheme 29: Synthesis of combretastatin D-4 (4) by Harras and co-workers [57].
Scheme 30: Formal synthesis of combretastatin D-1 (1) by Harras and co-workers [57].
Scheme 31: Synthesis of 11-O-methylcorniculatolide A (5) by Raut and co-workers [69].
Scheme 32: Synthesis of isocorniculatolide A (7) and O-methylated isocorniculatolide A 8 by Raut and co-worker...
Scheme 33: Synthesis of isocorniculatolide B (10) and hydroxyisocorniculatolide B 175 by Kim and co-workers [71].
Scheme 34: Synthesis of compound 9, 178, and 11 by Kim and co-workers [71].
Scheme 35: Synthesis of combretastatin D-2 prodrug salts [55].
Figure 2: ED50 values of the combretastatin D family against murine P388 lymphocytic leukemia cell line (appr...
Figure 3: IC50 of compounds against α-glucosidase [19].
Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions
- Hao Guo,
- Yu-Fei Ao,
- De-Xian Wang and
- Qi-Qiang Wang
Beilstein J. Org. Chem. 2022, 18, 486–496, doi:10.3762/bjoc.18.51
- ][10][11][12][13][14]. Among which, macrocyclic compounds have attracted extensive attentions due to their enzyme-mimicking cavity and preorganized binding sites [4][6][15][16]. Various macrocyclic compounds including the privileged scaffolds like cyclodextrins [17][18][19], calixarenes [20][21][22][23
Graphical Abstract
Figure 1: Design of PKS-inspired multifunctional amino-thiourea macrocycle catalysts.
Scheme 1: Synthesis of tetraamino-bisthiourea chiral macrocycles M1–M12. The synthesis of M1, M5, M7, and M8 ...
Scheme 2: Substrate scope of isatin imines. Reaction conditions: 6 (0.2 mmol), 7a (0.3 mmol), and 5 mol % M3 ...
Scheme 3: Substrate scope of MAHTs. Reaction conditions: 6a (0.2 mmol), 7 (0.3 mmol), and 5 mol % M3 in 2 mL ...
Figure 2: Proposed catalytic mechanism.
Progress and challenges in the synthesis of sequence controlled polysaccharides
- Giulio Fittolani,
- Theodore Tyrikos-Ergas,
- Denisa Vargová,
- Manishkumar A. Chaube and
- Martina Delbianco
Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129
- )-glucosamine macrocyclic compounds [265]. The iterative glycosylation of N-Phth protected 2-deoxy-2-aminothioglycosides allowed for the combinatorial synthesis of short oligoglucosamines having β(1–6) and/or β(1–4)-linkages [263]. Automated solution-phase synthesis of β(1–6)-glucosamine oligosaccharides
Graphical Abstract
Figure 1: Overview of the methods available for the synthesis of polysaccharides. For each method, advantages...
Figure 2: Overview of the classes of polysaccharides discussed in this review. Each section deals with polysa...
Scheme 1: Enzymatic and chemical polymerization approaches provide cellulose oligomers with a non-uniform dis...
Scheme 2: AGA of a collection of cellulose analogues obtained using BBs 6–9. Specifically placed modification...
Figure 3: Chemical structure of the different branches G, X, L, F commonly found in XGs. Names are given foll...
Scheme 3: AGA of XG analogues with defined side chains. The AGA cycle includes coupling (TMSOTf), Fmoc deprot...
Figure 4: Synthetic strategies and issues associated to the formation of the β(1–3) linkage.
Scheme 4: Convergent synthesis of β(1–3)-glucans using a regioselective glycosylation strategy.
Scheme 5: DMF-mediated 1,2-cis glycosylation. A) General mechanism and B) examples of α-glucans prepared usin...
Scheme 6: Synergistic glycosylation strategy employing a nucleophilic modulation strategy (TMSI and Ph3PO) in...
Scheme 7: Different approaches to produce xylans. A) Polymerization techniques including ROP, and B) enzymati...
Scheme 8: A) Synthesis of arabinofuranosyl-decorated xylan oligosaccharides using AGA. Representative compoun...
Scheme 9: Chemoenzymatic synthesis of COS utilizing a lysozyme-catalyzed transglycosylation reaction followed...
Scheme 10: Synthesis of COS using an orthogonal glycosylation strategy based on the use of two different LGs.
Scheme 11: Orthogonal N-PGs permitted the synthesis of COS with different PA.
Scheme 12: AGA of well-defined COS with different PA using two orthogonally protected BBs. The AGA cycle inclu...
Scheme 13: A) AGA of β(1–6)-N-acetylglucosamine hexasaccharide and dodecasaccharide. AGA includes cycles of co...
Figure 5: ‘Double-faced’ chemistry exemplified for ᴅ-Man and ʟ-Rha. Constructing β-Man linkages is considerab...
Figure 6: Implementation of a capping step after each glycosylation cycle for the AGA of a 50mer oligomannosi...
Scheme 14: AGA enabled the synthesis of a linear α(1–6)-mannoside 100mer 93 within 188 h and with an average s...
Scheme 15: The 151mer branched polymannoside was synthesized by a [30 + 30 + 30 + 30 + 31] fragment coupling. ...
Figure 7: PG stereocontrol strategy to obtain β-mannosides. A) The mechanism of the β-mannosylation reaction ...
Scheme 16: A) Mechanism of 1,2-cis stereoselective glycosylation using ManA donors. Once the ManA donor is act...
Figure 8: A) The preferred 4H3 conformation of the gulosyl oxocarbenium ion favors the attack of the alcohol ...
Scheme 17: AGA of type I rhamnans up to 16mer using disaccharide BB 115 and CNPiv PG. The AGA cycle includes c...
Figure 9: Key BBs for the synthesis of the O-antigen of Bacteroides vulgatus up to a 128mer (A) and the CPS o...
Figure 10: Examples of type I and type II galactans synthesized to date.
Figure 11: A) The DTBS PG stabilizes the 3H4 conformation of the Gal oxocarbenium ion favoring the attack of t...
Figure 12: Homogalacturonan oligosaccharides synthesized to date. Access to different patterns of methyl-ester...
Figure 13: GlfT2 from Mycobacterium tuberculosis catalyzes the sequential addition of UPD-Galf donor to a grow...
Figure 14: The poor reactivity of acceptor 137 hindered a stepwise synthesis of the linear galactan backbone a...
Scheme 18: AGA of a linear β(1–5) and β(1–6)-linked galactan 20mer. The AGA cycle includes coupling (NIS/TfOH)...
Figure 15: The 92mer arabinogalactan was synthesized using a [31 + 31 + 30] fragment coupling between a 31mer ...
Scheme 19: Synthesis of the branched arabinofuranose fragment using a six component one-pot synthesis. i) TTBP...
Figure 16: A) Chemical structure and SNFG of the representative disaccharide units forming the GAG backbones, ...
Figure 17: Synthetic challenges associated to the H/HS synthesis.
Scheme 20: Degradation of natural heparin and heparosan generated valuable disaccharides 150 and 151 that can ...
Scheme 21: A) The one-step conversion of cyanohydrin 156 to ʟ-iduronamide 157 represent the key step for the s...
Scheme 22: A) Chemoenzymatic synthesis of heparin structures, using different types of UDP activated natural a...
Scheme 23: Synthesis of the longest synthetic CS chain 181 (24mer) using donor 179 and acceptor 180 in an iter...
Scheme 24: AGA of a collection of HA with different lengths. The AGA cycle includes coupling (TfOH) and Lev de...
Insight into functionalized-macrocycles-guided supramolecular photocatalysis
- Minzan Zuo,
- Krishnasamy Velmurugan,
- Kaiya Wang,
- Xueqi Tian and
- Xiao-Yu Hu
Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15
- substrate with suitable binding sites for photochemical transformations. Cyclodextrin-based photocatalysis CDs represent a family of macrocyclic compounds in which the ᴅ-glucopyranose units are connected to each other via an α-1,4-glycosidic bond. The inside of a cyclodextrin is a hydrophobic cavity, and
Graphical Abstract
Figure 1: Chemical structures of representative macrocycles.
Figure 2: Ba2+-induced intermolecular [2 + 2]-photocycloaddition of crown ether-functionalized substrates 1 a...
Figure 3: Energy transfer system constructed of a BODIPY–zinc porphyrin–crown ether triad assembly bound to a...
Figure 4: The sensitizer 5 was prepared by a flavin–zinc(II)–cyclen complex for the photooxidation of benzyl ...
Figure 5: Enantiodifferentiating Z–E photoisomerization of cyclooctene sensitized by a chiral sensitizer as t...
Figure 6: Structures of the modified CDs as chiral sensitizing hosts. Adapted with permission from [24], Copyrigh...
Figure 7: Supramolecular 1:1 and 2:2 complexations of AC with the cationic β-CD derivatives 16–21 and subsequ...
Figure 8: Construction of the TiO2–AuNCs@β-CD photocatalyst. Republished with permission of The Royal Society...
Figure 9: Visible-light-driven conversion of benzyl alcohol to H2 and a vicinal diol or to H2 and benzaldehyd...
Figure 10: (a) Structures of CDs, (b) CoPyS, and (c) EY. Republished with permission of The Royal Society of C...
Figure 11: Conversion of CO2 to CO by ReP/HO-TPA–TiO2. Republished with permission of The Royal Society of Che...
Figure 12: Thiacalix[4]arene-protected TiO2 clusters for H2 evolution. Reprinted with permission from [37], Copyri...
Figure 13: 4-Methoxycalix[7]arene film-based TiO2 photocatalytic system. Reprinted from [38], Materials Today Chem...
Figure 14: (a) Photodimerization of 6-methylcoumarin (22). (b) Catalytic cycle for the photodimerization of 22...
Figure 15: Formation of a supramolecular PDI–CB[7] complex and structures of monomers and the chain transfer a...
Figure 16: Ternary self-assembled system for photocatalytic H2 evolution (a) and structure of 27 (b). Figure 16 reprodu...
Figure 17: Structures of COP-1, CMP-1, and their substrate S-1 and S-2.
Figure 18: Supramolecular self-assembly of the light-harvesting system formed by WP5, β-CAR, and Chl-b. Reprod...
Figure 19: Photocyclodimerization of AC based on WP5 and WP6.
The interaction between cucurbit[8]uril and baicalein and the effect on baicalein properties
- Xiaodong Zhang,
- Jun Xie,
- Zhiling Xu,
- Zhu Tao and
- Qianjun Zhang
Beilstein J. Org. Chem. 2020, 16, 71–77, doi:10.3762/bjoc.16.9
- hydrophobic rigid cavity [32] (Figure 1). cucurbit[n]urils have a unique combination of properties including rigid highly symmetric structures, relatively large hydrophobic cavities and high thermal and chemical stability [33][34]. Cucurbit[n]urils are a type of macrocyclic drug carrier similar to macrocyclic
- compounds such as calixarenes, crown ethers and cyclodextrins, which can be used to form a stable inclusion complex with the drug, and improving the bioavailability of the drug [34][35]. Herein, we describe the results of the investigations of host–guest interactions between BALE and Q[8] in an aqueous
Graphical Abstract
Figure 1: Chemical structures of baicalein (left), cucurbit[8]uril (right).
Figure 2: The possible interaction model for Q[8] and baicalein.
Figure 3: 1H NMR spectra (400 MHz) of Q[8] (a), baicalein (b) and BALE–Q[8] (1:1) (c) recorded in DCl.
Figure 4: The absorption spectra of BALE upon the addition of Q[8] under different conditions [10 mol·L−1 HCl...
Figure 5: IR spectra of Q[8] (a), BALE (b), a physical mixture of Q[8]-BALE (NQ[8]/NBALE = 1:1) (c) and the B...
Figure 6: DTA spectra of BALE (a), Q[8] (b), a physical mixture Q[8]-BALE (NQ[8]/NBALE = 1:1) (c) and the BAL...
Figure 7: The stability curve of UV–vis absorption obtained for an isoconcentration of BALE and the BALE–Q[8]...
Figure 8: The phase solubility graph obtained for BALE in Q[8] at λ = 270 nm.
Figure 9: The clearance rate curve (A) and clearance time curve (B) of ABTS+· upon increasing the concentrati...
Figure 10: The release curves of BALE and BALE–Q[8].
Attempted synthesis of a meta-metalated calix[4]arene
- Christopher D. Jurisch and
- Gareth E. Arnott
Beilstein J. Org. Chem. 2019, 15, 1996–2002, doi:10.3762/bjoc.15.195
- yielding transformations to azide and 1,2,3-triazole derivatives which may have application in other areas of research. Keywords: calixarene; inherent chirality; mesoionic carbene; mononitration; ruthenacycle; Introduction Calix[4]arenes are a class of diverse macrocyclic compounds which have been the
Graphical Abstract
Figure 1: Inherent chirality generated by meta-substitution – the two structures are non-superposable mirror ...
Figure 2: General approach by Albrecht for MIC directed cyclometalation via C–H activation; M = Ru(II), Ir(II...
Figure 3: Concept of cyclometalated calix[4]arene target.
Scheme 1: Synthesis of model mesoionic carbene 5.
Scheme 2: Attempted Ullmann-coupling to give monoazide 7.
Scheme 3: Synthesis of monoazidocalix[4]arene 7 under optimized conditions.
Scheme 4: Synthesis of the putative calix[4]arene mesoionic carbene ruthenium complex 13.
Figure 4: High-resolution mass spectrum (ESI+) of putative ruthenacycle calix[4]arene 13.
Complexation of chiral amines by resorcin[4]arene sulfonic acids in polar media – circular dichroism and diffusion studies of chirality transfer and solvent dependence
- Bartosz Setner and
- Agnieszka Szumna
Beilstein J. Org. Chem. 2019, 15, 1913–1924, doi:10.3762/bjoc.15.187
- a hydrophobic effect, while the other one has a more directional character, or application of multidentate interaction sites [3]. Macrocyclic compounds with persistent hydrophobic cavities constitute a fundamental class of scaffolds for the construction of supramolecular host–guest complexes in
- cyclodextrines, which, when unmodified, interact with a wide range of hydrophobic guests albeit with low general selectivity and enantioselectivity in particular [6]. In this paper we present a group of synthetic macrocyclic compounds – resorcin[4]arene sulfonic acids (RSAs) and analyze their interactions with
Graphical Abstract
Figure 1: Structures of the compounds used in this study and labelling scheme for NMR spectra.
Figure 2: Spectra of complexes [1(LysOMe)2], [1(ArgOMe)2], [1(HisOMe)2]: 1H NMR (a–g) and ROESY (h–j) in meth...
Figure 3: CD (a) and UV (b) spectra of complexes [1(LysOMe)2], [1(PheOMe)2], [1(ValOMe)2], [1(ArgOMe)2], and [...
Figure 4: DOSY spectra of 1 (a), [1(LysOMe)2] (b), [1(ArgOMe)2] (c), [1(HisOMe)2] (d) and [LysOMe + 1(LysOMe)2...
Figure 5: 1H NMR spectra of 1 (a), LysOMe (b), 1H NMR and DOSY spectra of [1(LysOMe)2] (insets show the shape...
Figure 6: 1H NMR spectra of (R)-2 (a); [1((R)-2] (b); [1 + 1((R)-2] (c) (insets show the shape of signals f, ...
Figure 7: 1H NMR and DOSY spectra of (R)-2 (a); [1(R)-2] (b) (inset show the shape signals f, DMSO-d6, 298K, ...
Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments
- Guojuan Li,
- Chunying Fan,
- Guo Cheng,
- Wanhua Wu and
- Cheng Yang
Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164
- assigned to the excimer emission of Py (Figure S23, Supporting Information File 1) [54]. Conclusion Two new planar chiral macrocyclic hosts P5A-DPA and P5A-Py were synthesized by grafting two fluorophore pigments (DPA or Py) on pillar[5]arene through CuAAC “click” reaction. The new macrocyclic compounds
Graphical Abstract
Scheme 1: Preparation of A1/A2-difunctionalized pillar[5]arenes (P5A-DPA and P5A-Py) by click reactions. Reag...
Figure 1: UV–vis absorption (a) and fluorescence emission spectra (b) of Py-6, P5A-Py (λex = 420 nm) and DPA-6...
Figure 2: (a) Fluorescence decay curves of Py-6 and P5A-Py at 450 nm and (b) fluorescence decay curves of DPA...
Figure 3: (a) Chiral HPLC traces of P5A-DPA, (b), (c) the first and second fractions of P5A-DPA, detected by ...
Figure 4: (a) CD, (b) UV–vis and (c) fluorescence spectra of the RP5A-DPA (20 μM) in THF and THF/H2O solvent ...
Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response
- Yu-Ying Wang,
- Yong Kong,
- Zhe Zheng,
- Wen-Chao Geng,
- Zi-Yi Zhao,
- Hongwei Sun and
- Dong-Sheng Guo
Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139
- supramolecular cavities [25]. Calixarenes are the third generation of macrocyclic compounds composed of phenolic units bridged with methylene groups at the o-positions of phenolic hydroxy groups [9]. We have focused on molecular recognition and self-assembly of water-soluble calixarene derivatives for a long
Graphical Abstract
Scheme 1: (a) Schematic illustration of IDA. The addition of an analyte competitor leads to switch-on or swit...
Scheme 2: (a) The chemical structure of GC5A and schematic illustration of the binding between the luminescen...
Figure 1: Direct fluorescence titrations (λex = 350 nm) of 2,6-TNS (1.0 μM) (a) and 1,8-ANS (1.0 μM) (c) with...
Figure 2: (a) Direct fluorescence titration (λex = 327 nm) of P-TPE (1.0 μM) with GC5A in HEPES buffer (10 mM...
Figure 3: (a) Direct fluorescence titration (λex = 371 nm) of TPS (1.0 μM) with GC5A in HEPES buffer (10 mM, ...
Figure 4: (a) Direct fluorescence titration (λex = 465 nm) of Ru(dcbpy)3 (1.0 μM) with GC5A. (b) Direct absor...
N-doped carbon dots covalently functionalized with pillar[5]arenes for Fe3+ sensing
- Jia Gao,
- Ming-Xue Wu,
- Dihua Dai,
- Zhi Cai,
- Yue Wang,
- Wenhui Fang,
- Yan Wang and
- Ying-Wei Yang
Beilstein J. Org. Chem. 2019, 15, 1262–1267, doi:10.3762/bjoc.15.123
- macrocyclic compounds, especially new macrocyclic arenes, have become one of the research hotspots in supramolecular chemistry [11][12][13][14]. Among them pillarenes as a relatively new family of pillar-shaped members discovered a decade ago have played a key role due to their unique conformations
Graphical Abstract
Scheme 1: Schematic illustration of the synthesis of CCDs and its use for Fe3+ sensing.
Figure 1: TEM images of a) CCDs and b) CN-dots. c) UV–vis spectra of CP5, CN-dots, and CCDs. d) FTIR spectra ...
Figure 2: a) Photographs of CN-dots and CCDs in aqueous media in natural light, and under excitation with a U...
Figure 3: Fluorescence quenching degrees of a) CCDs and b) CN-dots in the presence of different metal ions. T...
Molecular recognition using tetralactam macrocycles with parallel aromatic sidewalls
- Dong-Hao Li and
- Bradley D. Smith
Beilstein J. Org. Chem. 2019, 15, 1086–1095, doi:10.3762/bjoc.15.105
- effect; macrocycles; rotaxane; supramolecular; Review 1. Introduction A large fraction of host–guest chemistry research uses macrocyclic compounds as the host molecules [1][2]. There are several reasons for this circumstance. Macrocycles are often relatively easy to synthesize and they have inherently
Graphical Abstract
Scheme 1: Chemical structures of the tetralactam host macrocycles that are covered by this review.
Figure 1: X-ray crystal structures of various squaraine rotaxanes show that the macrocycle bridging units con...
Figure 2: X-ray crystal structures of macrocycles that are representative of the tetralactam systems in Scheme 1. In ...
Scheme 2: Synthetic yields of [2]rotaxanes with different dumbbell-shaped templates and tetralactam A as the ...
Scheme 3: Supramolecular picture of the amide-bond-formation step that clips tetralactam A around a biscarbon...
Figure 3: Selected X-ray structures of [2]rotaxanes with tetralactam A as the surrounding macrocycle reported...
Figure 4: (a) Chemical structures of squaraine, thiosquaraine, croconaine, and acene guests that can bind ins...
Scheme 4: Complex stabilization due to guest back folding and aromatic stacking with the surrounding tetralac...
Figure 5: (a) Shape and electrostatic comparison of squaraine C4O2 core (left) with anionic square planar met...
Figure 6: Chemical structures of a) acetylcholine chloride, 26+·Cl−, (b) trimethyl-p-cyanobenzylammonium chlo...
Figure 7: a) Chemical structure of β-D-glucopyranose and the solid-state structure of its complexes with macr...
Host–guest complexes of conformationally flexible C-hexyl-2-bromoresorcinarene and aromatic N-oxides: solid-state, solution and computational studies
- Rakesh Puttreddy,
- Ngong Kodiah Beyeh,
- S. Maryamdokht Taimoory,
- Daniel Meister,
- John F. Trant and
- Kari Rissanen
Beilstein J. Org. Chem. 2018, 14, 1723–1733, doi:10.3762/bjoc.14.146
- , aiding in the binding of polar guests such as N-oxides. Keywords: aromatic N-oxides; C–H···π Interactions; ditopic receptors; endo/exo complexation; host–guest chemistry; resorcinarenes; Introduction Resorcinarenes are macrocyclic compounds with a bowl-shaped cavity stabilised by circular
Graphical Abstract
Figure 1: The chemical structures of C-ethyl-2-bromoresorcinarene (BrC2), C-propyl-2-bromoresorcinarene (BrC3...
Figure 2: X-ray crystal structures of (a) 3@BrC6, (b) 4@BrC6, (c) 5@BrC6, (d) 6@BrC6, (e) 7@BrC6, (f) 8@BrC6,...
Figure 3: Comparison of X-ray crystal structures (a) 3@BrC2, (c) 3@BrC3, and (e) 3@BrC6 and their DFT-based o...
Figure 4: (a) The negative potential localised on the N-oxide oxygen in 3@BrC6 and, (b) the positive charge d...
Figure 5: An expansion of the 1H NMR (6.6 mM at 298 K, 500 MHz) of BrC6 complexes with 3. Spectra are produce...
Synthesis of diamido-bridged bis-pillar[5]arenes and tris-pillar[5]arenes for construction of unique [1]rotaxanes and bis-[1]rotaxanes
- Ying Han,
- Li-Ming Xu,
- Cui-Yun Nie,
- Shuo Jiang,
- Jing Sun and
- Chao-Guo Yan
Beilstein J. Org. Chem. 2018, 14, 1660–1667, doi:10.3762/bjoc.14.142
- ], cyclodextrin [24][25][26], calixarene [27][28][29] and pillararene have been successfully employed as the wheel subcomponent. Pillararenes are new star macrocyclic compounds with aromatic rings para-bridged by methylene units and have unique tubular shape rather than cone [30][31][32]. In recent years, an
Graphical Abstract
Scheme 1: Synthesis of pillar[5]arene mono(oxyalkoxy)benzoic acids 3a–c.
Figure 1: single crystal structure of pillar[5]arene 2a.
Figure 2: Single crystal structure of pillar[5]arene 2f.
Scheme 2: Synthesis of diamido-bridged bis-pillar[5]arenes 5a–d.
Figure 3: The 2D NOSEY spectrum of bis-pillar[5]arene 5d.
Scheme 3: Synthesis of pillar[5]arene di(oxyalkoxy)benzoic acid 8.
Figure 4: Single crystal structure of pillar[5]arene 7.
Scheme 4: Synthesis of diamido-bridged tris-pillar[5]arenes 9a–d.
Figure 5: The 2D NOSEY spectra of tris-pillar[5]arene 9d.
Synthesis of a sucrose-based macrocycle with unsymmetrical monosaccharides "arms"
- Karolina Tiara,
- Mykhaylo A. Potopnyk and
- Sławomir Jarosz
Beilstein J. Org. Chem. 2018, 14, 634–641, doi:10.3762/bjoc.14.50
- ; Introduction Chiral macrocyclic compounds play an important role in supramolecular and biological systems [1][2]. Many of them serve as convenient receptors for cations [3], anions [4], ion pairs [5], neutral molecules [6] etc. Binaphthols [7][8][9], amino acids [10], chiral diamines [11][12], carbohydrates
Graphical Abstract
Scheme 1: Synthesis of macrocyclic derivative 4.
Figure 1: Possible route to sucrose cryptands 6.
Figure 2: Possible route to dienes of type 9.
Scheme 2: Unsuccessful attempts to amines 12a and 13b.
Scheme 3: Syntheses of "elongated" amines 17 and 18.
Scheme 4: Synthesis of macrocycle 25.
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
- : higher carbon sugars; reductive amination; sucrose; Introduction Carbohydrates, because of their availability in a variety of optical pure forms, are particularly useful in planning and executing the synthesis of chiral macrocyclic compounds [1][2][3][4][5]. In this context, polyhydroxylated derivatives
Graphical Abstract
Figure 1: Previous synthesis of a C12-higher sugar 1 and its application in the preparation of a polyhydroxyl...
Scheme 1: Preparation of C12-aminoalditol 10.
Figure 2: Examples of highly functionalized sucrose derivatives from our laboratory.
Scheme 2: Preparation of a sucrose molecule with a higher aminoalditol pendant.
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
- , Himachal Pradesh, 176 061, India 10.3762/bjoc.13.110 Abstract An efficient, eco-compatible diversity-oriented synthesis (DOS) approach for the generation of library of sugar embedded macrocyclic compounds with various ring size containing 1,2,3-triazole has been developed. This concise strategy involves
- with many functional groups found application in pharmaceuticals, agrochemicals, cosmetics and materials science [1][2][3][4]. Carbohydrate-embedded macrocycles represent an important class of macrocyclic compounds in which at least two bonds from a monosaccharide residue form a part of the macrocyclic
- macrocyclic compounds (pair phase). In the pair phase, CuAAC adducts were cyclized using a Ru-catalyzed metathesis reaction utilizing Grubbs second generation catalysts under greener reaction conditions (Figure 1). Build phase: preparation of building blocks The alkyne–alkene (1a–f) and azide–alkene (2a–d
Graphical Abstract
Figure 1: Build-couple-pair (B/C/P) strategy for macrocycles.
Figure 2: Different building blocks used for DOS.
Scheme 1: Cycloaddition reaction of alkyne-azide building block.
Scheme 2: Acetylation of macrocycle 4m.
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
Graphical Abstract
Figure 1: The named transformations considered in this review.
Scheme 1: The Baeyer–Villiger oxidation.
Scheme 2: The general mechanism of the peracid-promoted Baeyer–Villiger oxidation.
Scheme 3: General mechanism of the Lewis acid-catalyzed Baeyer–Villiger rearrangement.
Scheme 4: The theoretically studied mechanism of the BV oxidation reaction promoted by H2O2 and the Lewis aci...
Scheme 5: Proton movements in the transition states of the Baeyer–Villiger oxidation.
Scheme 6: The dependence of the course of the Baeyer–Villiger oxidation on the type of O–O-bond cleavage in t...
Scheme 7: The acid-catalyzed Baeyer–Villiger oxidation of cyclic epoxy ketones 22.
Scheme 8: Oxidation of isophorone oxide 29.
Scheme 9: Synthesis of acyl phosphate 32 from acyl phosphonate 31.
Scheme 10: Synthesis of aflatoxin B2 (36).
Scheme 11: The Baeyer–Villiger rearrangement of ketones 37 to lactones 38.
Scheme 12: Synthesis of 3,4-dimethoxybenzoic acid (40) via Baeyer–Villiger oxidation.
Scheme 13: Oxone transforms α,β-unsaturated ketones 43 into vinyl acetates 44.
Scheme 14: The Baeyer–Villiger oxidation of ketones 45 using diaryl diselenide and hydrogen peroxide.
Scheme 15: Baeyer–Villiger oxidation of (E)-2-methylenecyclobutanones.
Scheme 16: Oxidation of β-ionone (56) by H2O2/(BnSe)2 with formation of (E)-2-(2,6,6-trimethylcyclohex-1-en-1-...
Scheme 17: The mechanism of oxidation of ketones 58a–f by hydrogen peroxide in the presence of arsonated polys...
Scheme 18: Oxidation of ketone (58b) by H2O2 to 6-methylcaprolactone (59b) catalyzed by Pt complex 66·BF4.
Scheme 19: Oxidation of ketones 67 with H2O2 in the presence of [(dppb}Pt(µ-OH)]22+.
Scheme 20: The mechanism of oxidation of ketones 67 in the presence of [(dppb}Pt(µ-OH)]22+ and H2O2.
Scheme 21: Oxidation of benzaldehydes 69 in the presence of the H2O2/MeReO3 system.
Scheme 22: Oxidation of acetophenones 72 in the presence of the H2O2/MeReO3 system.
Scheme 23: Baeyer–Villiger oxidation of 2-adamantanone (45c) in the presence of Sn-containing mesoporous silic...
Scheme 24: Aerobic Baeyer–Villiger oxidation of ketones 76 using metal-free carbon.
Scheme 25: A regioselective Baeyer-Villiger oxidation of functionalized cyclohexenones 78 into a dihydrooxepin...
Scheme 26: The oxidation of aldehydes and ketones 80 by H2O2 catalyzed by Co4HP2Mo15V3O62.
Scheme 27: The cleavage of ketones 82 with hydrogen peroxide in alkaline solution.
Scheme 28: Oxidation of ketones 85 to esters 86 with H2O2–urea in the presence of KHCO3.
Scheme 29: Mechanism of the asymmetric oxidation of cyclopentane-1,2-dione 87a with the Ti(OiPr)4/(+)DET/t-BuO...
Scheme 30: The oxidation of cis-4-tert-butyl-2-fluorocyclohexanone (93) with m-chloroperbenzoic acid.
Scheme 31: The mechanism of the asymmetric oxidation of 3-substituted cyclobutanone 96a in the presence of chi...
Scheme 32: Enantioselective Baeyer–Villiger oxidation of cyclic ketones 98.
Scheme 33: Regio- and enantioselective Baeyer–Villiger oxidation of cyclic ketones 101.
Scheme 34: The proposed mechanism of the Baeyer–Villiger oxidation of acetal 105f.
Scheme 35: Synthesis of hydroxy-10H-acridin-9-one 117 from tetramethoxyanthracene 114.
Scheme 36: The Baeyer–Villiger oxidation of the fully substituted pyrrole 120.
Scheme 37: The Criegee rearrangement.
Scheme 38: The mechanism of the Criegee reaction of a peracid with a tertiary alcohol 122.
Scheme 39: Criegee rearrangement of decaline ethylperoxoate 127 into ketal 128.
Scheme 40: The ionic cleavage of 2-methoxy-2-propyl perester 129.
Scheme 41: The Criegee rearrangement of α-methoxy hydroperoxide 136.
Scheme 42: Synthesis of enol esters and acetals via the Criegee rearrangement.
Scheme 43: Proposed mechanism of the transformation of 1-hydroperoxy-2-oxabicycloalkanones 147a–d.
Scheme 44: Transformation of 3-hydroxy-1,2-dioxolanes 151 into diketone derivatives 152.
Scheme 45: Criegee rearrangement of peroxide 153 with the mono-, di-, and tri-O-insertion.
Scheme 46: The sequential Criegee rearrangements of adamantanes 157a,b.
Scheme 47: Synthesis of diaryl carbonates 160a–d from triarylmethanols 159a–d through successive oxygen insert...
Scheme 48: The synthesis of sesquiterpenes 162 from ketone 161 with a Criegee rearrangement as one key step.
Scheme 49: Synthesis of trans-hydrindan derivatives 164, 165.
Scheme 50: The Hock rearrangement.
Scheme 51: The general scheme of the cumene process.
Scheme 52: The Hock rearrangement of aliphatic hydroperoxides.
Scheme 53: The mechanism of solvolysis of brosylates 174a–c and spiro cyclopropyl carbinols 175a–c in THF/H2O2....
Scheme 54: The fragmentation mechanism of hydroperoxy acetals 178 to esters 179.
Scheme 55: The acid-catalyzed rearrangement of phenylcyclopentyl hydroperoxide 181.
Scheme 56: The peroxidation of tertiary alcohols in the presence of a catalytic amount of acid.
Scheme 57: The acid-catalyzed reaction of bicyclic secondary alcohols 192 with hydrogen peroxide.
Scheme 58: The photooxidation of 5,6-disubstituted 3,4-dihydro-2H-pyrans 196.
Scheme 59: The oxidation of tertiary alcohols 200a–g, 203a,b, and 206.
Scheme 60: Transformation of functional peroxide 209 leading to 2,3-disubstitued furans 210 in one step.
Scheme 61: The synthesis of carbazoles 213 via peroxide rearrangement.
Scheme 62: The construction of C–N bonds using the Hock rearrangement.
Scheme 63: The synthesis of moiety 218 from 217 which is a structural motif in the antitumor–antibiotic of CC-...
Scheme 64: The in vivo oxidation steps of cholesterol (219) by singlet oxygen.
Scheme 65: The proposed mechanism of the rearrangement of cholesterol-5α-OOH 220.
Scheme 66: Photochemical route to artemisinin via Hock rearrangement of 223.
Scheme 67: The Kornblum–DeLaMare rearrangement.
Scheme 68: Kornblum–DeLaMare transformation of 1-phenylethyl tert-butyl peroxide (225).
Scheme 69: The synthesis 4-hydroxyenones 230 from peroxide 229.
Scheme 70: The Kornblum–DeLaMare rearrangement of peroxide 232.
Scheme 71: The reduction of peroxide 234.
Scheme 72: The Kornblum–DeLaMare rearrangement of endoperoxide 236.
Scheme 73: The rearrangement of peroxide 238 under Kornblum–DeLaMare conditions.
Scheme 74: The proposed mechanism of rearrangement of peroxide 238.
Scheme 75: The Kornblum–DeLaMare rearrangement of peroxides 242a,b.
Scheme 76: The base-catalyzed rearrangements of bicyclic endoperoxides having electron-withdrawing substituent...
Scheme 77: The base-catalyzed rearrangements of bicyclic endoperoxides 249a,b having electron-donating substit...
Scheme 78: The base-catalyzed rearrangements of bridge-head substituted bicyclic endoperoxides 251a,b.
Scheme 79: The Kornblum–DeLaMare rearrangement of hydroperoxide 253.
Scheme 80: Synthesis of β-hydroxy hydroperoxide 254 from endoperoxide 253.
Scheme 81: The amine-catalyzed rearrangement of bicyclic endoperoxide 263.
Scheme 82: The base-catalyzed rearrangement of meso-endoperoxide 268 into 269.
Scheme 83: The photooxidation of 271 and subsequent Kornblum–DeLaMare reaction.
Scheme 84: The Kornblum–DeLaMare rearrangement as one step in the oxidation reaction of enamines.
Scheme 85: The Kornblum–DeLaMare rearrangement of 3,5-dihydro-1,2-dioxenes 284, 1,2-dioxanes 286, and tert-but...
Scheme 86: The Kornblum–DeLaMare rearrangement of epoxy dioxanes 290a–d.
Scheme 87: Rearrangement of prostaglandin H2 292.
Scheme 88: The synthesis of epicoccin G (297).
Scheme 89: The Kornblum–DeLaMare rearrangement used in the synthesis of phomactin A.
Scheme 90: The Kornblum–DeLaMare rearrangement in the synthesis of 3H-quinazolin-4-one 303.
Scheme 91: The Kornblum–DeLaMare rearrangement in the synthesis of dolabriferol (308).
Scheme 92: Sequential transformation of 3-substituted 2-pyridones 309 into 3-hydroxypyridine-2,6-diones 311 in...
Scheme 93: The Kornblum–DeLaMare rearrangement of peroxide 312 into hydroxy enone 313.
Scheme 94: The Kornblum–DeLaMare rearrangement in the synthesis of polyfunctionalized carbonyl compounds 317.
Scheme 95: The Kornblum–DeLaMare rearrangement in the synthesis of (Z)-β-perfluoroalkylenaminones 320.
Scheme 96: The Kornblum–DeLaMare rearrangement in the synthesis of γ-ketoester 322.
Scheme 97: The Kornblum–DeLaMare rearrangement in the synthesis of diterpenoids 326 and 328.
Scheme 98: The synthesis of natural products hainanolidol (331) and harringtonolide (332) from peroxide 329.
Scheme 99: The synthesis of trans-fused butyrolactones 339 and 340.
Scheme 100: The synthesis of leucosceptroid C (343) and leucosceptroid P (344) via the Kornblum–DeLaMare rearra...
Scheme 101: The Dakin oxidation of arylaldehydes or acetophenones.
Scheme 102: The mechanism of the Dakin oxidation.
Scheme 103: A solvent-free Dakin reaction of aromatic aldehydes 356.
Scheme 104: The organocatalytic Dakin oxidation of electron-rich arylaldehydes 358.
Scheme 105: The Dakin oxidation of electron-rich arylaldehydes 361.
Scheme 106: The Dakin oxidation of arylaldehydes 358 in water extract of banana (WEB).
Scheme 107: A one-pot approach towards indolo[2,1-b]quinazolines 364 from indole-3-carbaldehydes 363 through th...
Scheme 108: The synthesis of phenols 367a–c from benzaldehydes 366a-c via acid-catalyzed Dakin oxidation.
Scheme 109: Possible transformation paths of the highly polarized boric acid coordinated H2O2–aldehyde adduct 3...
Scheme 110: The Elbs oxidation of phenols 375 to hydroquinones.
Scheme 111: The mechanism of the Elbs persulfate oxidation of phenols 375 affording p-hydroquinones 376.
Scheme 112: Oxidation of 2-pyridones 380 under Elbs persulfate oxidation conditions.
Scheme 113: Synthesis of 3-hydroxy-4-pyridone (384) via an Elbs oxidation of 4-pyridone (382).
Scheme 114: The Schenck rearrangement.
Scheme 115: The Smith rearrangement.
Scheme 116: Three main pathways of the Schenck rearrangement.
Scheme 117: The isomerization of hydroperoxides 388 and 389.
Scheme 118: Trapping of dioxacyclopentyl radical 392 by oxygen.
Scheme 119: The hypothetical mechanism of the Schenck rearrangement of peroxide 394.
Scheme 120: The autoxidation of oleic acid (397) with the use of labeled isotope 18O2.
Scheme 121: The rearrangement of 18O-labeled hydroperoxide 400 under an atmosphere of 16O2.
Scheme 122: The rearrangement of the oleate-derived allylic hydroperoxides (S)-421 and (R)-425.
Scheme 123: Mechanisms of Schenck and Smith rearrangements.
Scheme 124: The rearrangement and cyclization of 433.
Scheme 125: The Wieland rearrangement.
Scheme 126: The rearrangement of bis(triphenylsilyl) 439 or bis(triphenylgermyl) 441 peroxides.
Scheme 127: The oxidative transformation of cyclic ketones.
Scheme 128: The hydroxylation of cyclohexene (447) in the presence of tungstic acid.
Scheme 129: The oxidation of cyclohexene (447) under the action of hydrogen peroxide.
Scheme 130: The reaction of butenylacetylacetone 455 with hydrogen peroxide.
Scheme 131: The oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 132: The proposed mechanism for the oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 133: The rearrangement of ozonides.
Scheme 134: The acid-catalyzed oxidative rearrangement of malondialdehydes 462 under the action of H2O2.
Scheme 135: Pathways of the Lewis acid-catalyzed cleavage of dialkyl peroxides 465 and ozonides 466.
Scheme 136: The mechanism of the transformation of (tert-butyldioxy)cyclohexanedienones 472.
Scheme 137: The synthesis of Vitamin K3 from 472a.
Scheme 138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Scheme 139: The rearrangement of hydroperoxide 485 to form diketone 486.
Scheme 140: The base-catalyzed rearrangement of cyclic peroxides 488a–g.
Scheme 141: Synthesis of chiral epoxides and aldols from peroxy hemiketals 491.
Scheme 142: The multistep transformation of (R)-carvone (494) to endoperoxides 496a–e.
Scheme 143: The decomposition of anthracene endoperoxide 499.
Scheme 144: Synthesis of esters 503 from aldehydes 501 via rearrangement of peroxides 502.
Scheme 145: Two possible paths for the base-promoted decomposition of α-azidoperoxides 502.
Scheme 146: The Story decomposition of cyclic diperoxide 506a.
Scheme 147: The Story decomposition of cyclic triperoxide 506b.
Scheme 148: The thermal rearrangement of endoperoxides A into diepoxides B.
Scheme 149: The transformation of peroxide 510 in the synthesis of stemolide (511).
Scheme 150: The possible mechanism of the rearrangement of endoperoxide 261g.
Scheme 151: The photooxidation of indene 517.
Scheme 152: The isomerization of ascaridole (523).
Scheme 153: The isomerization of peroxide 525.
Scheme 154: The thermal transformation of endoperoxide 355.
Scheme 155: The photooxidation of cyclopentadiene (529) at a temperature higher than 0 °C.
Scheme 156: The thermal rearrangement of endoperoxides 538a,b.
Scheme 157: The transformation of peroxides 541.
Scheme 158: The thermal rearrangements of strained cyclic peroxides.
Scheme 159: The thermal rearrangement of diacyl peroxide 551 in the synthesis of C4-epi-lomaiviticin B core 553....
Scheme 160: The 1O2 oxidation of tryptophan (554) and rearrangement of dioxetane intermediate 555.
Scheme 161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Scheme 162: The proposed mechanism of the Fe(II)-promoted rearrangement of 557a–c.
Scheme 163: The reaction of dioxolane 563 with Fe(II) sulfate.
Scheme 164: Fe(II)-promoted rearrangement of 1,2-dioxane 565.
Scheme 165: Fe(II) cysteinate-promoted rearrangement of 1,2-dioxolane 568.
Scheme 166: The transformation of 1,2-dioxanes 572a–c under the action of FeCl2.
Scheme 167: Fe(II) cysteinate-promoted transformation of tetraoxane 574.
Scheme 168: The CoTPP-catalyzed transformation of bicyclic endoperoxides 600a–d.
Scheme 169: The CoTPP-catalyzed transformation of epoxy-1,2-dioxanes.
Scheme 170: The Ru(II)-catalyzed reactions of 1,4-endoperoxide 261g.
Scheme 171: The Ru(II)-catalyzed transformation as a key step in the synthesis of elyiapyrone A (610) from 1,4-...
Scheme 172: Peroxides with antimalarial activity.
Scheme 173: The interaction of iron ions with artemisinin (616).
Scheme 174: The interaction of FeCl2 with 1,2-dioxanes 623, 624.
Scheme 175: The mechanism of reaction 623 and 624 with Fe(II)Cl2.
Scheme 176: The reaction of bicyclic natural endoperoxides G3-factors 631–633 with FeSO4.
Scheme 177: The transformation of terpene cardamom peroxide 639.
Scheme 178: The different ways of the cleavage of tetraoxane 643.
Scheme 179: The LC–MS analysis of interaction of tetraoxane 646 with iron(II)heme 647.
Scheme 180: The rearrangement of 3,6-epidioxy-1,10-bisaboladiene (EDBD, 649).
Scheme 181: Easily oxidized substrates.
Scheme 182: Biopathway of synthesis of prostaglandins.
Scheme 183: The reduction and rearrangements of isoprostanes.
Scheme 184: The partial mechanism for linoleate 658 oxidation.
Scheme 185: The transformation of lipid hydroperoxide.
Scheme 186: The acid-catalyzed cleavage of the product from free-radical oxidation of cholesterol (667).
Scheme 187: Two pathways of catechols oxidation.
Scheme 188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme...
Scheme 189: Carotinoides 679 cleavage by carotenoid cleavage dioxygenases.
Interactions of cyclodextrins and their derivatives with toxic organophosphorus compounds
- Sophie Letort,
- Sébastien Balieu,
- William Erb,
- Géraldine Gouhier and
- François Estour
Beilstein J. Org. Chem. 2016, 12, 204–228, doi:10.3762/bjoc.12.23
- to these characterization methods, molecular modelling analysis can afford further clues to select the suitable CD derivative for one specific pesticide. This could also support the rational design of new macrocyclic compounds able to strongly interact with organophosphates. The structure of the
Graphical Abstract
Figure 1: Structure of NOPs.
Figure 2: Examples of structures of NOPs.
Figure 3: Structures of pesticides studied in the literature as guest to form an inclusion complex with CDs.
Figure 4: Structures of pesticides sensitive to the presence of CDs.
Scheme 1: The hydrolysis mechanism of substrate (S) in presence of a cyclodextrin (CD).
Figure 5: Structures of the different stereoisomers of G agents.
Scheme 2: Reaction mechanism of CD accelerated decomposition of organophosphorus compound (PX).
Scheme 3: Proposed degradation mechanism of cyclosarin by β-CD [72].
Figure 6: Schematic representations of β-CD and TRIMEB.
Scheme 4: Synthetic pathways to 6-monosubstituted CD derivatives.
Scheme 5: Synthetic pathways to 2-monosubstituted CD by an iodosobenzoate group.
Scheme 6: Synthetic pathways to 2-monosubstituted CDs with N–OH derivatives.
Scheme 7: Synthetic pathways to 3-monosubstituted CDs.
Scheme 8: Synthetic pathways to 3-homodisubstituted CDs.
Scheme 9: Synthetic pathways to 2,3-heterodisubstituted CDs.
Synthesis and photophysical characteristics of polyfluorene polyrotaxanes
- Aurica Farcas,
- Giulia Tregnago,
- Ana-Maria Resmerita,
- Pierre-Henri Aubert and
- Franco Cacialli
Beilstein J. Org. Chem. 2015, 11, 2677–2688, doi:10.3762/bjoc.11.288
- conjugated polymers [16][17][18][19][20][26][27][28][29][30][31][32][33][34][35][36][37][38]. The first step in the preparation of conjugated polyrotaxanes is the threading of macrocyclic compounds (hosts) onto linear chains (guests), when a thermodynamically unstable inclusion complex (IC) is obtained. A
Graphical Abstract
Scheme 1: Synthetic route of 3·TM-βCD and 3·TM-γCD polyrotaxanes, and the non-rotaxane counterpart 3.
Figure 1: 1H NMR spectrum of the polyrotaxane 3·TM-βCD copolymer in CDCl3.
Figure 2: DSC traces on second heating scan of 3, 3·TM-βCD and 3·TM-γCD compounds.
Figure 3: Optical properties of 3·TM-γCD (dotted line), 3·TM-βCD (dashed line) and 3 (solid line) polymers: a...
Figure 4: CV of 3 (a), 3·TM-βCD (b) and 3·TM-γCD (c) in 0.1 M tetrabutylammonium perchlorate (TBAClO4)/ACN so...
Figure 5: Representative AFM images obtained over 3 × 3 µm2 areas of the non-rotaxane 3 (a), 3·TM-βCD (b) and ...
Diversity-oriented synthesis of analogues of the novel macrocyclic peptide FR-225497 through late stage functionalization
- Jyotiprasad Mukherjee,
- Suman Sil and
- Shital Kumar Chattopadhyay
Beilstein J. Org. Chem. 2015, 11, 2487–2492, doi:10.3762/bjoc.11.270
- [8], macrocyclic compounds are currently expanding the medicinal chemistry space [9][10]. Macrocyclic natural products [11] with significant levels of biological activity, and their analogues [12] are therefore receiving attention as targets for diversity-oriented synthesis. A class of cyclic tetra
Graphical Abstract
Figure 1: Structure of FR-225497 (4) and related cyclic tetrapeptides.
Figure 2: Synthetic planning for the design of analogues of 4.
Scheme 1: Preparation of the macrocyclic template 13.
Scheme 2: Synthesis of nor-FR225497 (15).
Scheme 3: Synthesis of oxygenated ethyl vinyl ketones.
Scheme 4: Synthesis of analogues of FR-225497.
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
- 139 by using the Wurtz coupling as a key step (Scheme 20). Metathesis Alkyne metathesis reaction: In 2010, Murphy and Jarikote [139] have developed a useful protocol for assembling non-natural macrocyclic compounds containing carbohydrates. Compound 140 was prepared in several steps and was further
Graphical Abstract
Figure 1: General representation of cyclophanes.
Figure 2: cyclophanes one or more with heteroatom.
Figure 3: Metathesis catalysts 12–17 and C–C coupling catalyst 18.
Figure 4: Natural products containing the cyclophane skeleton.
Figure 5: Turriane family of natural products.
Scheme 1: Synthesis of [3]ferrocenophanes through Mannich reaction. Reagents and conditions: (i) excess HNMe2...
Scheme 2: Synthesis of cyclophanes through Michael addition. Reagents and conditions: (i) xylylene dibromide,...
Scheme 3: Synthesis of normuscopyridine analogue 37 through an oxymercuration–oxidation strategy. Reagents an...
Scheme 4: Synthesis of tribenzocyclotriyne 39 through Castro–Stephens coupling reaction. Reagents and conditi...
Scheme 5: Synthesis of cyclophane 43 through Glaser–Eglinton coupling. Reagents and conditions: (i) 9,10-bis(...
Scheme 6: Synthesis of the macrocyclic C-glycosyl cyclophane through Glaser coupling. Reagents and conditions...
Scheme 7: Synthesis of cyclophane-containing complex 49 through Glaser–Eglinton coupling reaction. Reagents a...
Scheme 8: Synthesis of cyclophane 53 through Glaser–Eglinton coupling. Reagents and conditions: (i) K2CO3, ac...
Figure 6: Cyclophanes 54–56 that have been synthesized through Glaser–Eglinton coupling.
Figure 7: Synthesis of tetrasubstituted [2.2]paracyclophane 57 and chiral cyclophyne 58 through Eglinton coup...
Scheme 9: Synthesis of cyclophane through Glaser–Hay coupling reaction. Reagents and conditions: (i) CuCl2 (1...
Scheme 10: Synthesis of seco-C/D ring analogs of ergot alkaloids through intramolecular Heck reaction. Reagent...
Scheme 11: Synthesis of muscopyridine 73 via Kumada coupling. Reagents and conditions: (i) 72, THF, ether, 20 ...
Scheme 12: Synthesis of the cyclophane 79 via McMurry coupling. Reagents and conditions: (i) 75, decaline, ref...
Scheme 13: Synthesis of stilbenophane 81 via McMurry coupling. Reagents and conditions: (i) TiCl4, Zn, pyridin...
Scheme 14: Synthesis of stilbenophane 85 via McMurry coupling. Reagents and conditions: (i) NBS (2 equiv), ben...
Figure 8: List of cyclophanes prepared via McMurry coupling reaction as a key step.
Scheme 15: Synthesis of paracyclophane by cross coupling involving Pd(0) catalyst. Reagents and conditions: (i...
Scheme 16: Synthesis of the cyclophane 112 via the pinacol coupling and 113 by RCM. Reagents and conditions: (...
Scheme 17: Synthesis of cyclophane derivatives 122a–c via Sonogoshira coupling. Reagents and conditions: (i) C...
Scheme 18: Synthesis of cyclophane 130 via Suzuki–Miyaura reaction as a key step. Reagents and conditions: (i)...
Scheme 19: Synthesis of the mycocyclosin via Suzuki–Miyaura cross coupling. Reagents and conditions: (i) benzy...
Scheme 20: Synthesis of cyclophanes via Wurtz coupling reaction Reagents and conditions: (i) PhLi, Et2O, C6H6,...
Scheme 21: Synthesis of non-natural glycophanes using alkyne metathesis. Reagents and conditions: (i) G-I (12)...
Figure 9: Synthesis of cyclophanes via ring-closing alkyne metathesis.
Scheme 22: Synthesis of crownophanes by cross-enyne metathesis. Reagents and conditions: (i) G-II (13), 5 mol ...
Scheme 23: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 24: Synthesis of cyclophane 159 derivatives via SM cross-coupling and RCM. Reagents and conditions: (i)...
Scheme 25: Sexithiophene synthesis via cross metathesis. Reagents and conditions: (i) 161, Pd(PPh3)4, K2CO3, T...
Scheme 26: Synthesis of pyrrole-based cyclophane using enyne metathesis. Reagents and conditions: (i) Se, chlo...
Scheme 27: Synthesis of macrocyclic derivatives by RCM. Reagents and conditions: (i) G-I/G-II, CH2Cl2, 0.005 M...
Scheme 28: Synthesis of enantiopure β-lactam-based dienyl bis(dihydrofuran) 179. Reagents and conditions: (i) ...
Scheme 29: Synthesis of a [1.1.6]metaparacyclophane derivative 183 via SM cross coupling. Reagents and conditi...
Scheme 30: Synthesis of a [1.1.6]metaparacyclophane derivative 190 via SM cross coupling. Reagents and conditi...
Scheme 31: Template-promoted synthesis of cyclophanes involving RCM. Reagents and conditions: (i) acenaphthene...
Scheme 32: Synthesis of [3.4]cyclophane derivatives 200 via SM cross coupling and RCM. Reagents and conditions...
Figure 10: Examples for cyclophanes synthesized by RCM.
Scheme 33: Synthesis of the longithorone C framework assisted by fluorinated auxiliaries. Reagents and conditi...
Scheme 34: Synthesis of the longithorone framework via RCM. Reagents and conditions: (i) 213, NaH, THF, rt, 10...
Scheme 35: Synthesis of floresolide B via RCM as a key step. Reagents and conditions: (i) G-II (13, 0.1 equiv)...
Scheme 36: Synthesis of normuscopyridine (223) by the RCM strategy. Reagents and condition: (i) Mg, THF, hexen...
Scheme 37: Synthesis of muscopyridine (73) via RCM. Reagents and conditions: (i) 225, NaH, THF, 0 °C to rt, 1....
Scheme 38: Synthesis of muscopyridine (73) via RCM strategy. Reagents and conditions: (i) NaH, n-BuLi, 5-bromo...
Scheme 39: Synthesis of pyridinophane derivatives 223 and 245. Reagents and conditions: (i) PhSO2Na, TBAB, CH3...
Scheme 40: Synthesis of metacyclophane derivatives 251 and 253. Reagents and conditions: (i) 240, NaH, THF, rt...
Scheme 41: Synthesis of normuscopyridine and its higher analogues. Reagents and conditions: (i) alkenyl bromid...
Scheme 42: Synthesis of fluorinated ferrocenophane 263 via a [2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 43: Synthesis of [2.n]metacyclophanes 270 via a [2 + 2] cycloaddition. Reagents and conditions: (i) Ac2...
Scheme 44: Synthesis of metacyclophane 273 by a [2 + 2 + 2] co-trimerization. Reagents and conditions: (i) [Rh...
Scheme 45: Synthesis of paracyclophane 276 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: ...
Scheme 46: Synthesis of cyclophane 278 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: (i) ...
Scheme 47: Synthesis of cyclophane 280 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) [(Rh(cod)(...
Scheme 48: Synthesis of taxane framework by a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) Cp(CO)2 ...
Scheme 49: Synthesis of cyclophane 284 and 285 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditio...
Scheme 50: Synthesis of pyridinophanes 293a,b and 294a,b via a [2 + 2 + 2] cycloaddition. Reagents and conditi...
Scheme 51: Synthesis of pyridinophanes 296 and 297 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 52: Synthesis of triazolophane by a 1,3-dipolar cycloaddition. Reagents and conditions: (i) propargyl b...
Scheme 53: Synthesis of glycotriazolophane 309 by a click reaction. Reagents and conditions: (i) LiOH, H2O, Me...
Figure 11: Cyclophanes 310 and 311 prepared via click chemistry.
Scheme 54: Synthesis of cyclophane via the Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C, 12 h...
Scheme 55: Synthesis of [6,6]metacyclophane by a Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C...
Scheme 56: Synthesis of cyclophanes by a Dötz benzannulation. Reagents and conditions: (i) THF, 65 °C, 3 h; (i...
Scheme 57: Synthesis of muscopyridine (73) via an intramolecular DA reaction of ketene. Reagents and condition...
Scheme 58: Synthesis of bis[10]paracyclophane 336 via Diels–Alder reaction. Reagents and conditions: (i) DMAD,...
Scheme 59: Synthesis of [8]paracyclophane via DA reaction. Reagents and conditions: (i) maleic anhydride, 3–5 ...
Scheme 60: Biomimetic synthesis of (−)-longithorone A. Reagents and conditions: (i) Me2AlCl, CH2Cl2, −20 °C, 7...
Scheme 61: Synthesis of sporolide B (349) via a [4 + 2] cycloaddition reaction. Reagents and conditions: (i) P...
Scheme 62: Synthesis of the framework of (+)-cavicularin (352) via a [4 + 2] cycloaddition. Reagents and condi...
Scheme 63: Synthesis of oxazole-containing cyclophane 354 via Beckmann rearrangement. Reagents and conditions:...
Scheme 64: Synthesis of cyclophanes 360a–c via benzidine rearrangement. Reagents and conditions: (i) 356a–d, K2...
Scheme 65: Synthesis of cyclophanes 365a–c via benzidine rearrangement. Reagents and conditions: (i) BocNHNH2,...
Scheme 66: Synthesis of metacyclophane 367 via Ciamician–Dennstedt rearrangement. Reagents and conditions: (i)...
Scheme 67: Synthesis of cyclophane by tandem Claisen rearrangement and RCM as key steps. Reagents and conditio...
Scheme 68: Synthesis of cyclophane derivative 380. Reagents and conditions: (i) K2CO3, CH3CN, allyl bromide, r...
Scheme 69: Synthesis of metacyclophane via Cope rearrangement. Reagents and conditions: (i) MeOH, NaBH4, rt, 1...
Scheme 70: Synthesis of cyclopropanophane via Favorskii rearrangement. Reagents and conditions: (i) Br2, CH2Cl2...
Scheme 71: Cyclophane 389 synthesis via photo-Fries rearrangement. Reagents and conditions: (i) DMAP, EDCl/CHCl...
Scheme 72: Synthesis of normuscopyridine (223) via Schmidt rearrangement. Reagents and conditions: (i) ethyl s...
Scheme 73: Synthesis of crownophanes by tandem Claisen rearrangement. Reagents and conditions: (i) diamine, Et3...
Scheme 74: Attempted synthesis of cyclophanes via tandem Claisen rearrangement and RCM. Reagents and condition...
Scheme 75: Synthesis of muscopyridine via alkylation with 2,6-dimethylpyridine anion. Reagents and conditions:...
Scheme 76: Synthesis of cyclophane via Friedel–Craft acylation. Reagents and conditions: (i) CS2, AlCl3, 7 d, ...
Scheme 77: Pyridinophane 418 synthesis via Friedel–Craft acylation. Reagents and conditions: (i) 416, AlCl3, CH...
Scheme 78: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) NBS, A...
Scheme 79: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) BEMP, ...
Scheme 80: Cyclophane synthesis by coupling with TosMIC. Reagents and conditions: (i) (a) ClCH2OCH3, TiCl4, CS2...
Scheme 81: Synthesis of diaza[32]cyclophanes and triaza[33]cyclophanes. Reagents and conditions: (i) DMF, NaH,...
Scheme 82: Synthesis of cyclophane 439 via acyloin condensation. Reagents and conditions: (i) Na, xylene, 75%;...
Scheme 83: Synthesis of multibridged binuclear cyclophane 442 by aldol condensation. Reagents and conditions: ...
Scheme 84: Synthesis of various macrolactones. Reagents and conditions: (i) iPr2EtN, DMF, 77–83%; (ii) TBDMSCl...
Scheme 85: Synthesis of muscone and muscopyridine via Yamaguchi esterification. Reagents and conditions: (i) 4...
Scheme 86: Synthesis of [5]metacyclophane via a double elimination reaction. Reagents and conditions: (i) LiBr...
Figure 12: Cyclophanes 466–472 synthesized via Hofmann elimination.
Scheme 87: Synthesis of cryptophane via Baylis–Hillman reaction. Reagents and conditions: (i) methyl acrylate,...
Scheme 88: Synthesis of cyclophane 479 via double Chichibabin reaction. Reagents and conditions: (i) excess 478...
Scheme 89: Synthesis of cyclophane 483 via double Chichibabin reaction. Reagents and conditions: (i) 481, OH−;...
Scheme 90: Synthesis of cyclopeptide via an intramolecular SNAr reaction. Reagents and conditions: (i) TBAF, T...
Scheme 91: Synthesis of muscopyridine (73) via C-zip ring enlargement reaction. Reagents and conditions: (i) H...
Figure 13: Mechanism of the formation of compound 494.
Scheme 92: Synthesis of indolophanetetraynes 501a,b using the Nicholas reaction as a key step. Reagents and co...
Scheme 93: Synthesis of cyclophane via radical cyclization. Reagents and conditions: (i) cyclododecanone, phen...
Scheme 94: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 95: Cyclophane synthesis via Wittig reaction. Reagents and conditions: (i) LiOEt (2.1 equiv), THF, −78 ...
Figure 14: Representative examples of cyclophanes synthesized via Wittig reaction.
Scheme 96: Synthesis of the [6]paracyclophane via isomerization of Dewar benzene. Reagents and conditions: (i)...
Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels
- César A. Estévez,
- José Ramón Isasi,
- Eneko Larrañeta and
- Itziar Vélaz
Beilstein J. Org. Chem. 2014, 10, 3127–3135, doi:10.3762/bjoc.10.330
- nanocarriers, they have the ability to hold/release drugs as a function of pH [9]. Cyclodextrins (CD) are macrocyclic compounds consisting of several glucose units linked by α-D-1,4-glycosidic bonds. Despite their high solubility in water, the internal cavity of cyclodextrins is non-polar and these compounds
Graphical Abstract
Figure 1: Inclusion complex (polypseudorotaxane) between α-cyclodextrins and reverse Tetronics.
Figure 2: 90R4/α-CD gels loaded with lactase. Octablock Tetronic molecules (grey) are threaded by CDs (red) f...
Figure 3: FTIR spectra of Tetronic 90R4, α-CD, lactase and T25a10 complex.
Figure 4: Release profiles of lactase from T25a10 (open circles) and T15a10 (filled circles) at pH 6 from a) ...
Figure 5: Contribution of diffusion (open circles) and erosion (filled circles) mechanisms from polymers a) T...
Figure 6: Chemical structure of a reverse Tetronic.
Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism
- Joscha Vollmeyer,
- Friederike Eberhagen,
- Sigurd Höger and
- Stefan-S. Jester
Beilstein J. Org. Chem. 2014, 10, 2774–2782, doi:10.3762/bjoc.10.294
- the role of intraannular substituents on the 2D supramolecular surface patterns of macrocyclic compounds. Therefore, in addition to the concentration-driven conformational polymorphism that is yet attributed to a distinct extraannular substitution pattern as discussed above, we evaluate the role of
Graphical Abstract
Figure 1: (a), (b) Two distinguishable packings of alkyl chains on cutouts of graphite are shown with the car...
Figure 2: (a)–(c) Schematic structure of a hexagonal shape-persistent macrocycle with extraannular alkoxy cha...
Figure 3: (a)–(c) Shape-persistent macrocycles with an empty cavity (1), an apolar interior (undecyl diether ...
Figure 4: Scanning tunneling microscopy images and supramolecular models of (a)–(c) porous (= polymorph A) an...
Figure 5: (a)–(e): Schematic structure of the shape-persistent macrocycle 1 (as a representative of the serie...
