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

• -O-benzylsucrose with different unsaturated monosaccharide units is presented. Such a highly functionalized intermediate was cyclized under RCM conditions to afford a macrocyclic derivative containing a 31-membered ring in 26% yield. Keywords: chiral macrocycles; ring-closing metathesis; sucrose

• ; 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

• [13], etc. are usually applied as building blocks for construction of such type of compounds. We are engaged in the synthesis of such macrocyclic derivatives containing the most common natural disaccharide, sucrose [14][15]. Several different classes of macrocyclic derivatives, including: crown [16

Recent developments in the asymmetric Reformatsky-type reaction

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 325–344, doi:10.3762/bjoc.14.21

• total synthesis of naturally occurring 11-membered macrocyclic lactam cebulactam A1 [34]. In the presence of SmI2 in THF at reflux, chiral amide 41 underwent an intramolecular Reformatsky reaction to give the corresponding alcohol 42 in 84% yield as a couple of diastereomers (Scheme 17). The latter

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

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

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

• of a polynucleotide (interacting with the polycationic branches) and a further bioactive/drug molecule (included into the host cavity). The critical examination of the available literature suggests that one main drawback of this approach is the fact that the syntheses of the tailored macrocyclic

Sulfation and amidinohydrolysis in the biosynthesis of giant linear polyenes

• Hui Hong,
• Markiyan Samborskyy,
• Katsiaryna Usachova,
• Katharina Schnatz and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2017, 13, 2408–2415, doi:10.3762/bjoc.13.238

• Streptomyces neyagawaensis (Scheme 1), is a potent inhibitor of the fibrinogen receptor, which suggests an even wider potential utility for such compounds [8][9]. We have previously shown that in the biosynthesis of giant macrocyclic antifungal polyketides (so-called marginolactones) compounds bearing a

• medi4948. In contrast, when an authentic amidinohydrolase from the Streptomyces olivaceus Tü4018 strain producing the macrocyclic polyene desertomycin [10] was similarly cloned and expressed in S. malaysiensis DSM4137, it had no effect on the production of 1a and 1b (Figure S6, Supporting Information File

•  1), implying that these amidinotransferases operating on linear and macrocyclic polyenes do not have overlapping substrate specificities. Sequence alignment of amidinohydrolase Medi4948 with authentic ureohydrolases in the Protein Data Bank (PDB) (Figure S2, Supporting Information File 1) revealed

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• based on their unique functions. Phthalocyanines are also expected to be applied as functional dyes. A series of compounds having a macrocyclic π-conjugated system including porphyrin are known as functional dyes. In particular, phthalocyanines have a wide range of functions and are expected to serve as

Structural diversity in the host–guest complexes of the antifolate pemetrexed with native cyclodextrins: gas phase, solution and solid state studies

• Magdalena Ceborska,
• Magdalena Zimnicka,
• Aneta Aniela Kowalska,
• Kajetan Dąbrowa and
• Barbara Repeć

Beilstein J. Org. Chem. 2017, 13, 2252–2263, doi:10.3762/bjoc.13.222

• signal was observed (PTX#5 and H#6, Figure S14, Supporting Information File 1). Based on these results we assumed that guest molecule penetrates γ-CD from the wider rim and is inserted into the macrocyclic cavity. To further confirm these findings 1D measurements in DMSO-d6 were performed (see Supporting

• the guest (a: from left to right): pemetrexed (PTX) and folic acid (FA), and host molecules with increasing diameter of macrocyclic cavity (b: from left to right: α-, β- and γ-CDs). Dissociation efficiency curves of three CDs/PTX complexes. The ions were collided with nitrogen (pressure ca. 2 × 10−5

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

• which could eventually be used in the synthesis of macrocyclic derivatives. Sucrose, undoubtedly the most common disaccharide, has found applications in the synthesis of polymers [17] or surfactants [18]. There is also an increasing interest in the application of sucrose as a ‘normal’ chemical [16][19

Main group mechanochemistry

• Agota A. Gečiauskaitė and
• Felipe García

Beilstein J. Org. Chem. 2017, 13, 2068–2077, doi:10.3762/bjoc.13.204

• adamantoid P4(NR)6 frameworks. These species are synthesised by direct reaction of PCl3 with sterically unhindered amines RNH2 (R= Me, Et, iPr, Bz) [101] or by isomerization of their less thermodynamically-stable macrocyclic [{P(μ-NR)}2(μ-NR)]2 counterparts. In the latter, the isopropyl (iPr) substituted

p-tert-Butylthiacalix[4]arenes functionalized by N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide fragments: synthesis and binding of anionic guests

• Alena A. Vavilova and
• Ivan I. Stoikov

Beilstein J. Org. Chem. 2017, 13, 1940–1949, doi:10.3762/bjoc.13.188

• type of anion is needed. (Thia)calix[4]arene derivatives are a favorable platform for the design of such structures [24][25][26][27][28][29][30][31][32][33][34]. Due to their macrocyclic nature and the possibility to modify them in three different ways (upper and lower rims and bridge fragments), they

• containing N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide moieties at the lower rim The regioselective synthesis of p-tert-butylthiacalix[4]arenes partially substituted at the lower rim, is an important challenge because it allows the sequential functionalization of the macrocyclic platform with the

• protons of the macrocycle and the oxymethylene protons of N,N-diethylacetamide moiety indicate the presence of substituents on opposite sides of the macrocyclic ring. This fact, as well as the cross-peak due to the dipole–dipole interaction of protons of the hydroxy groups confirms the presence of the

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Molecular recognition of N-acetyltryptophan enantiomers by β-cyclodextrin

• Spyros D. Chatziefthimiou,
• Mario Inclán,
• Petros Giastas,
• Athanasios Papakyriakou,
• Konstantina Yannakopoulou and
• Irene M. Mavridis

Beilstein J. Org. Chem. 2017, 13, 1572–1582, doi:10.3762/bjoc.13.157

• with the (S)-enantiomer [14]. Induced host–guest fit, made possible by the macrocyclic flexibility of the permethylated CDs plays a crucial role in their capacity for chiral discrimination. Chiral recognition of amino acids and their derivatives by CDs has been also tested using phase-solubility

Towards open-ended evolution in self-replicating molecular systems

• Herman Duim and
• Sijbren Otto

Beilstein J. Org. Chem. 2017, 13, 1189–1203, doi:10.3762/bjoc.13.118

• members. Set I is therefore able to transfer information about its macrocyclic size to set II. This process bears a crude resemblance to how species originate in biology. Conclusion Self-replicating molecules have been remarkably hard to develop and after 30 years of research there are still only a

Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience

• Serge Pérez and
• Daniele de Sanctis

Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114

• -rhamnopyranosyl (1->3) α-L-rhamnopyranosyl (1->2) β-D-glucopyransyl (1->2) β-D-fucopyranoid linked to japinoli acid forming a 19-membered ring macrocyclic ester, extracted from Convolvulaceous species which have been used in traditional medicine throughout the world since ancient times. Small crystals, with

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

• potential of the new eco-compatible approach for the macrocyclic library generation. Keywords: carbohydrate; click chemistry; diversity-oriented synthesis; macrocycles; ring-closing metathesis; Introduction Macrocycles offer very complex molecular architectures with a diverse range of ring sizes decorated

• 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

Total syntheses of the archazolids: an emerging class of novel anticancer drugs

• Stephan Scheeff and
• Dirk Menche

Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108

• was planned which would likewise set the labile C2–C5 diene and thus concomitantly stabilize this functionality by macrocyclic constraints. Menche’s total synthesis of archazolid A Synthesis of the north-eastern fragment As shown in Scheme 3, the construction of the north-eastern fragment 5 relied on

• deprotection step. The Menche group then had considerable difficulties in closing the macrocyclic ring using an HWE reaction. Finally, the macrocylization could be realised by using NaH as a strong non-nucleophilic base. It proved essential to perform this reaction in the presence of molecular sieves to remove

• synthesis. Accordingly, they applied a Heck macrocyclization strategy for the total synthesis of archazolid B. As shown in Scheme 7, this strategy could be successfully implemented and the macrocyclic core of the target compound was obtained in useful yields by coupling of 38, which in turn was accessible

Inclusion complexes of β-cyclodextrin with tricyclic drugs: an X-ray diffraction, NMR and molecular dynamics study

• Franca Castiglione,
• Fabio Ganazzoli,
• Luciana Malpezzi,
• Andrea Mele,
• Walter Panzeri and
• Giuseppina Raffaini

Beilstein J. Org. Chem. 2017, 13, 714–719, doi:10.3762/bjoc.13.70

• )° for 1 and 2, respectively, where the figures in parentheses give the standard errors. The β-CD macrocyclic rings appear slightly distorted upon inclusion of the guest molecule. In the crystal, the arrangement of the complexes formed by 1 and 2 with β-CD are similar, being stacked head-to-head to form

• and refined with a riding model. Both complexes were found to crystallize in the solid state in 1:1 host–guest ratio with many partially disordered water molecules distributed in the intermolecular space outside the macrocyclic cavities. Full molecular and crystal data, together with the structural

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• template for design of complex molecules has become increasingly popular in pharmacology, supramolecular chemistry and nanoscience over recent years [4][5]. Many macrocyclic dimeric derivatives of bile acid were described [6][7][8]. As a rule, a route to the majority of macrocyclic structures requires

Novel β-cyclodextrin–eosin conjugates

• Gábor Benkovics,
• Damien Afonso,
• András Darcsi,
• Szabolcs Béni,
• Sabrina Conoci,
• Éva Fenyvesi,
• Lajos Szente,
• Milo Malanga and
• Salvatore Sortino

Beilstein J. Org. Chem. 2017, 13, 543–551, doi:10.3762/bjoc.13.52

• property can be utilized to protect the guest molecules from oxidation and degradation, to enhance their solubility and bioavailability, or to use the CD host as a drug carrier [1]. The potential application of these macrocyclic sugars in such pharmaceutical formulations required the understanding of the

Structure–efficiency relationships of cyclodextrin scavengers in the hydrolytic degradation of organophosphorus compounds

• Sophie Letort,
• Michaël Bosco,
• Benedetta Cornelio,
• Frédérique Brégier,
• Sébastien Daulon,
• Géraldine Gouhier and
• François Estour

Beilstein J. Org. Chem. 2017, 13, 417–427, doi:10.3762/bjoc.13.45

• study focusing on the impact of covalently bound functional groups to macrocyclic β-cyclodextrin that are involved in the OP hydrolysis. Four new derivatives 2–5 were prepared (Figure 3) for this purpose. Compared to analog 1, scavenger 2 has a longer linker between the iodosobenzoate group and the

Dimerization reactions of aryl selenophen-2-yl-substituted thiocarbonyl S-methanides as diradical processes: a computational study

• Michael L. McKee,
• Grzegorz Mlostoń,
• Katarzyna Urbaniak and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 410–416, doi:10.3762/bjoc.13.44

• pathway via a diradical intermediate leading to the formation of the unusual macrocyclic dimer 9 by computational methods. First calculations were made for phenyl selenophen-2-yl thiocarbonyl S-methanide (8A), which can undergo a 1,3-dipolar electrocyclization (1,3-ring closure) to form the thiirane 3a

• of thiobenzophenone S-methanide 1 (Ar1 = Ar2 = Ph). On the other hand, in the hetaryl functionalized thiocarbonyl S-methanide 8 the lowest activation energy was found for the C–C bond formation between C(2) atoms of the selenophen-2-yl ring, leading to the twelve-membered macrocyclic product 9

Polyketide stereocontrol: a study in chemical biology

• Kira J. Weissman

Beilstein J. Org. Chem. 2017, 13, 348–371, doi:10.3762/bjoc.13.39

• synthesis [4]), which incorporate both high functional group density and rich stereochemistry. These features, coupled with the fact that the majority of reduced polyketides are macrocyclic, result in significant in-built conformational constraints. As a consequence, these molecules present their diverse

Posttranslational isoprenylation of tryptophan in bacteria

• Masahiro Okada,
• Tomotoshi Sugita and
• Ikuro Abe

Beilstein J. Org. Chem. 2017, 13, 338–346, doi:10.3762/bjoc.13.37

• unknown at this time. Kawaguchipeptins A and B are members of the cyanobactin family and are macrocyclic undecapeptides with the cyclic amino acid sequence of [WLNGDNNWSTP]. They are produced by Microcystis aeruginosa NIES-88 (Figure 6) [52][53]. Kawaguchipeptin A contains one D-leucine and two prenylated

Interactions between photoacidic 3-hydroxynaphtho[1,2-b]quinolizinium and cucurbit[7]uril: Influence on acidity in the ground and excited state

• Jonas Becher,
• Daria V. Berdnikova,
• Darinka Dzubiel,
• Heiko Ihmels and
• Phil M. Pithan

Beilstein J. Org. Chem. 2017, 13, 203–212, doi:10.3762/bjoc.13.23

• this ligand increase by about two to three orders of magnitude, respectively, when bound to CB[7]. Keywords: azoniahetarenes; cucurbit[7]uril; heterocycles; photoacids; supramolecular photochemistry; Introduction The complexation of ligands by macrocyclic host molecules, such as crown ethers

Efficient access to β-vinylporphyrin derivatives via palladium cross coupling of β-bromoporphyrins with N-tosylhydrazones

• Vinicius R. Campos,
• Ana T. P. C. Gomes,
• Anna C. Cunha,
• Maria da Graça P. M. S. Neves,
• Vitor F. Ferreira and
• José A. S. Cavaleiro

Beilstein J. Org. Chem. 2017, 13, 195–202, doi:10.3762/bjoc.13.22

• fields, including medicine [1][2][3] , supramolecular chemistry [4][5][6] and catalysis [7][8][9][10]; their functionalization became a target for several research groups [11][12][13]. In particular, the insertion of functional groups into the macrocyclic core merits considerable attention due to the

Identification, synthesis and mass spectrometry of a macrolide from the African reed frog Hyperolius cinnamomeoventris

• Markus Menke,
• Pardha Saradhi Peram,
• Iris Starnberger,
• Walter Hödl,
• Gregory F.M. Jongsma,
• David C. Blackburn,
• Mark-Oliver Rödel,
• Miguel Vences and
• Stefan Schulz

Beilstein J. Org. Chem. 2016, 12, 2731–2738, doi:10.3762/bjoc.12.269

• , is usually not possible from an EI mass spectrum. In the article, we present the synthesis and for the first time elucidate the structure of macrolides from the frog family Hyperoliidae. Keywords: chemical communication; chiral gas chromatography; macrocyclic lactones; ring-closing metathesis

• ; pheromones; Introduction The lactone motif is found in many compounds that are used in chemical communication. Among them, macrocyclic lactones are an important class because of their biosynthetic availability and their inherent compound properties. During the biosynthesis of macrocyclic lactones, a fatty

• from Madagascar also use chemical cues. Macrocyclic lactones such as phoracantholide I (3), phoracantholide J (4) or gephyromantolide A (5), are released by males from femoral glands to serve as signals, often accompanied by secondary alcohols (Figure 1) [2][3][4]. Another frog family most likely using