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

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• used in Birch-type reductive alkylations of polynuclear aromatic compounds [36][37][38][39], as well as aromatic acids, and their esters and amides [40][41]. The structures of the obtained products 5ab–af were consistent with the proposed reaction scheme (Scheme 2). It corresponds to the introduction

Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

• Shulei Pan,
• Hang Jiang,
• Yanghui Zhang,
• Yu Zhang and
• Dushen Chen

Beilstein J. Org. Chem. 2016, 12, 1302–1308, doi:10.3762/bjoc.12.122

• research on the properties and application of tetraphenylene derivatives. Keywords: acetoxylation; carbonylation; halogenation; tetraphenylene; transition metal; Introduction Tetraphenylene (1) is one of the simplest motifs in the eight-membered ring aromatic compounds (Figure 1) [1][2]. Based on its

Synthesis and fluorosolvatochromism of 3-arylnaphtho[1,2-b]quinolizinium derivatives

• Phil M. Pithan,
• David Decker,
• Manlio Sutero Sardo,
• Giampietro Viola and
• Heiko Ihmels

Beilstein J. Org. Chem. 2016, 12, 854–862, doi:10.3762/bjoc.12.84

• even the intermolecular electron transfer reactions between electron rich aromatic compounds, such as naphthalene and phenanthrene, and the excited benzo[b]quinolizinium fluorophore were shown to be efficient processes [37]. The biaryl derivatives 6b–e exhibit fluorosolvatochromism that is

Gold-catalyzed direct alkynylation of tryptophan in peptides using TIPS-EBX

• Gergely L. Tolnai,
• Jonathan P. Brand and
• Jerome Waser

Beilstein J. Org. Chem. 2016, 12, 745–749, doi:10.3762/bjoc.12.74

• and unfolding, or protein engineering to install more accessible cysteines, are usually required. For these reasons, it is important to develop selective alkynylation methods in order to functionalize other amino acids. The direct C–H functionalization of aromatic compounds is an attractive method for

A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy

• Steven C. Zimmerman

Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14

• , Darryl Rideout (coincidentally a Madison West High School classmate), Alanna Schepartz, Alan Schwabacher, George Trainor, Craig Wilcox, and Jeff Winkler. Ron Breslow had broad interests, with projects ranging from developing artificial enzymes, to novel anti-aromatic compounds, to remote C–H activation

• complexing more structurally challenging organic guests such as nucleobases. We quickly discovered that in chloroform solution, 4 and its analogs could bind nitrated aromatic compounds, such as 2,4,7-trinitrofluorenone. Nitrated polycyclic aromatics and polynitrated fluorenones were known pollutants so Kurt

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

• Norbert Vida,
• Jiří Václavík and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12

• detected [15]. Interestingly, this reaction sequence is essentially identical to the aerobic microbial degradation of aromatic compounds, which involves hydroxylating oxygenase and ring-cleaving dioxygenase enzymes [16][17][18][19]. This sequence of reactions however, does not account for the presence of

• )acetic acid, which in aqueous solution exists in equilibrium with its enol form. Further experiments are underway to find out whether aerobic microbial degradation of SF5-substituted aromatic compounds follows the same pathway as our chemical oxidation method. Optimized geometries of transition states of

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

• Tsuyuka Sugiishi,
• Hideki Amii,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286

• . This report suggests that TFA can act as a trifluoromethyl source in the reaction with inactivated aromatic compounds, while the control of regioselectivity is difficult. Trifluoromethylation with difluorocarbene and fluoride ions The reaction system with ClCF2CO2Me/KF/CuI also generates CF3Cu in situ

Recent highlights in biosynthesis research using stable isotopes

• Jan Rinkel and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2015, 11, 2493–2508, doi:10.3762/bjoc.11.271

• classes including polyketides, non-ribosomal peptides, their hybrids, terpenoids, and aromatic compounds formed via the shikimate pathway. The text does not aim at a comprehensive overview, but instead a selection of recent important examples of isotope usage within biosynthetic studies is presented, with

• ], but these aspects will not be discussed here. Instead, this review highlights recent biosynthetic studies using isotopes from major classes of natural products including polyketides, non-ribosomal peptides, hybrids thereof, isoprenoids and a few aromatic compounds that arise via the shikimate pathway

• the mechanism via cation 66. This isotopically sensitive branching experiment shows the usefulness of labeling studies even in cases where two possible mechanisms lead to the same atom arrangement in the natural product. Aromatic compounds via the shikimate pathway Recently, a series of H218O-based

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• dissertation research focused on photo-induced reactions of perfluoroalkyl iodides and pentafluoroiodobenzene with arenes, aromatic ethers and amines and heterocycles. These reactions led to the perfluoroalkylation or pentafluorophenylation of the aromatic compounds. One series of reactions involved liquid

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• comparison in order to determine the structure of similar compounds. For instance, comparison of the 13C NMR data (Tables 1–5) of compounds 1–13 (Table 6) revealed the chemical shift of C-1 (δ 131.0) to be downfield when the B ring is aromatic (compounds 1, and 9, 11–13) [42][43][44][45][46][47][48][49][50

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• aryldiazonium tetrafluoroborates with pyridine and iodine resulted in aryl iodides. An efficient reaction was observed with electron-acceptor substituted aromatic compounds even with ortho-substituted derivatives. In the case of SF5-substituted iodobenzenes, the method is much more efficient than the classical

Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

• Mohamed Yacine Ameur Messaoud,
• Ghenia Bentabed-Ababsa,
• Madani Hedidi,
• Aïcha Derdour,
• Floris Chevallier,
• Yury S. Halauko,
• Oleg A. Ivashkevich,
• Vadim E. Matulis,
• Laurent Picot,
• Valérie Thiéry,
• Thierry Roisnel,
• Vincent Dorcet and
• Florence Mongin

Beilstein J. Org. Chem. 2015, 11, 1475–1485, doi:10.3762/bjoc.11.160

• 100 °C (1 equiv of base) [21] and in diethyl ether at −70 °C (2 equiv) [22]. In the course of the last fifteen years, combinations of lithium reagents and softer metal compounds have established themselves as appropriate tools to deproto-metallate sensitive aromatic compounds [23][24][25][26][27][28

• ], and for which the 1:1 LiTMP·2LiCl(±TMEDA)–Zn(TMP)2 composition was given [32], proved to be a ‘superbase’. Indeed, its reactivity is higher than that of the separate LiTMP and Zn(TMP)2) when used to functionalize sensitive aromatic compounds such as heterocycles [31][33][34][35][36][37][38][39][40][41

Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations

• Adriana K. Slavova-Kazakova,
• Silvia E. Angelova,
• Timur L. Veprintsev,
• Petko Denev,
• Davide Fabbri,
• Maria Antonietta Dettori,
• Maria Kratchanova,
• Vladimir V. Naumov,
• Aleksei V. Trofimov,
• Rostislav F. Vasil’ev,
• Giovanna Delogu and
• Vessela D. Kancheva

Beilstein J. Org. Chem. 2015, 11, 1398–1411, doi:10.3762/bjoc.11.151

• of favorable contacts with the protein compared to other aromatic compounds and, generally, stability under physiological conditions. It was reported [11] that the dehydrozingerone dimer 6 partially inhibits the aggregation process of alpha synuclein (AS), which is involved as misfolded protein in

Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

• Jerzy Zakrzewski and
• Bogumiła Huras

Beilstein J. Org. Chem. 2015, 11, 1155–1162, doi:10.3762/bjoc.11.130

• saturated aliphatic acids (instead of unsaturated ones as acrylates) are reacted with simple aromatic compounds (as benzene) in the presence of palladium(II) chloride [20]. Due to the important biological activity of cinnamates, the incorporation of a spin label moiety, particularly a nitroxyl fragment, is

Indolizines and pyrrolo[1,2-c]pyrimidines decorated with a pyrimidine and a pyridine unit respectively

• Marcel Mirel Popa,
• Emilian Georgescu,
• Mino R. Caira,
• Florentina Georgescu,
• Constantin Draghici,
• Raluca Stan,
• Calin Deleanu and
• Florea Dumitrascu

Beilstein J. Org. Chem. 2015, 11, 1079–1088, doi:10.3762/bjoc.11.121

• primary cycloadduct 19 which spontaneously rearranges and dehydrogenates under the reaction conditions, to the final aromatic compounds 20. X-ray crystal structures of the starting compounds 4-(2-pyridyl)pyrimidine (6) and 4-(4-pyridyl)pyrimidine (8) Full details of the structural solution and refinements

Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption

• Dominik Schmitt,
• Carolin Regenbrecht,
• Marius Hartmer,
• Florian Stecker and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2015, 11, 473–480, doi:10.3762/bjoc.11.53

• renewable feedstocks in the world [1][2][3]. Moreover, lignin represents the largest source of aromatic compounds among renewables and can be considered as non-food biomass. It usually occurs as a major waste fraction of the pulping industry on a multimillion ton scale [4]. This source has the potential to

Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

• Martin Popr,
• Sergey K. Filippov,
• Nikolai Matushkin,
• Juraj Dian and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2015, 11, 192–199, doi:10.3762/bjoc.11.20

• surface of polymeric Nafion® 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV–vis

• transport of aromatic compounds [30]. In this paper we report on a comprehensive study of the properties of the novel monosubstituted cationic CD derivative PEMPDA-β-CD (PErMethylated PropyleneDiAmine substituted). Its thermal stability is compared to the previously reported analogue PEMEDA-β-CD

A facile synthesis of functionalized 7,8-diaza[5]helicenes through an oxidative ring-closure of 1,1’-binaphthalene-2,2’-diamines (BINAMs)

• Youhei Takeda,
• Masato Okazaki,
• Yoshiaki Maruoka and
• Satoshi Minakata

Beilstein J. Org. Chem. 2015, 11, 9–15, doi:10.3762/bjoc.11.2

• polycyclic aromatic compounds, have been fascinating organic chemists over the last century since the first synthesis of azahelicenes was reported by Meisenheimer in 1903 [1], not only because of their aesthetically attractive structures, but also because of their unique properties arising from the helical

The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

• Volodymyr V. Tkachenko,
• Elena A. Muravyova,
• Sergey M. Desenko,
• Oleg V. Shishkin,
• Svetlana V. Shishkina,
• Dmytro O. Sysoiev,
• Thomas J. J. Müller and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2014, 10, 3019–3030, doi:10.3762/bjoc.10.320

• other hand, N-aryl-4-(2-hydroxyphenyl)-3,6-dimethylisoxazolo[5,4-b]pyridine-5-carboxamides 9e–g were allocated if the acetoacetamide had any non oxygen-containing ortho-substituent on the benzene ring (Table 3, entries 14, 15, 17, 18, 20, 21). It is worth mentioning that aromatic compounds 9e–g were

(2R,1'S,2'R)- and (2S,1'S,2'R)-3-[2-Mono(di,tri)fluoromethylcyclopropyl]alanines and their incorporation into hormaomycin analogues

• Armin de Meijere,
• Sergei I. Kozhushkov,
• Dmitrii S. Yufit,
• Christian Grosse,
• Marcel Kaiser and
• Vitaly A. Raev

Beilstein J. Org. Chem. 2014, 10, 2844–2857, doi:10.3762/bjoc.10.302

• classical resolution [41], enzymatic resolution in conjunction with HPLC [42], or HPLC separation of derived peptides [43], preparative HPLC separation on a chiral phase column [44], asymmetric synthesis from chiral precursors [45][46] including the stereoselective alkylation of aromatic compounds with

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• functional moiety is not prone to hydrolytic or enzymatic decay. Stable conjugation is an essential prerequisite for applications such as labelling or targeting. Here we report on the grafting of nitrogen-containing heterocyclic aromatic compounds using the Diels–Alder reaction of suitable starting materials

Effect of cyclodextrin complexation on phenylpropanoids’ solubility and antioxidant activity

• Miriana Kfoury,
• David Landy,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2014, 10, 2322–2331, doi:10.3762/bjoc.10.241

• and the competitor (methyl orange, MO). The results are summarized in Table 1 in comparison with values from the literature. The stoichiometry of all studied inclusion complexes was found to be 1:1 (CD:PP). This is in accordance with results generally obtained for aromatic compounds. The calculated Kf

Building complex carbon skeletons with ethynyl[2.2]paracyclophanes

• Ina Dix,
• Lidija Bondarenko,
• Peter G. Jones,
• Thomas Oeser and
• Henning Hopf

Beilstein J. Org. Chem. 2014, 10, 2013–2020, doi:10.3762/bjoc.10.209

• the growing use of ethynylcyclophanes as substrates for the preparation of carbon-rich organic compounds [3][4][5][6]. The use of ethynylaromatics for the synthesis of “extended aromatic compounds” is anything but new, as indicated by three of the smallest building blocks applied for this purpose: 1,2

Theoretical study of the adsorption of benzene on coinage metals

• Werner Reckien,
• Melanie Eggers and
• Thomas Bredow

Beilstein J. Org. Chem. 2014, 10, 1775–1784, doi:10.3762/bjoc.10.185

• crucial role for the adsorption of large aromatic compounds on metal surfaces [9][10][11]. This holds in particular for the adsorption on the coinage metals copper, silver and gold. Therefore, a theoretical treatment of this process requires methods that provide an accurate description of these weak

• adsorption of aromatic compounds. In the last years much effort has been directed to the development of DFT methods that eliminate this shortage [13][14][15][16][17][18][19][20][21][22][23][24]. One of them is a damped empirical correction called DFT-D3 which was proposed by Grimme et al. for molecular

• ][11][26]. However, a systematic comparison of the different DFT-D3 approaches is still missing. One aim of this work is the comparison of different DFT-D3 methods for the description of the adsorption of aromatic compounds on this surfaces. We therefore present a theoretical study of the adsorption of