First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

• Marwa Ayadi,
• Haitham Elleuch,
• Emmanuel Vrancken and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2906–2915, doi:10.3762/bjoc.12.290

• yields and selectivity, using cyclic MBH acetates as starting materials, in the presence of DMAP or imidazole as additives (Scheme 2, reaction 6). Moreover, it has been demonstrated that the presence of a nitrogen atom and a phosphonate moiety in multifunctional compounds may improve their synthetic and

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

• Tamás Zoltán Agócs,
• István Puskás,
• Erzsébet Varga,
• Mónika Molnár and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2016, 12, 2873–2882, doi:10.3762/bjoc.12.286

• regions in shortage of drinking water [2]. The recently recognized harmful xenobiotics (contaminants of emerging concern, such as pharmaceutical residues, personal care products, industrial additives) impose a high risk on the environment and also on human because they usually do not degrade in nature

• of the polymer. The concentrations of the model compounds were measured as a function of time and the half-life time values were calculated to characterize the reaction rate of the degradation. For comparison, the decomposition of the model compounds was measured also without any additives and in the

• in distilled water without any additives (Figure 6 and Table 4) and a slight enhancement in the degradation rate was obtained with nanoTiO2. In the presence of the polymer the rate of degradation decreased suggesting that the complex formation of ibuprofen has a protective effect. Using the CMBCD-P

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

• Pavel Nagorny and
• Zhankui Sun

Beilstein J. Org. Chem. 2016, 12, 2834–2848, doi:10.3762/bjoc.12.283

• halogenating agent (I2 or TMSI, 15 mol %). These additives may undergo activation by L26 to result in more Lewis acidic species that ionize benzylic alcohols. Alternatively, addition of I2 or TMSI may accomplish in situ transformation of benzylic alcohols to benzyl iodides. These intermediates underwent

Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I)

• Sem Raj Tamang and
• James D. Hoefelmeyer

Beilstein J. Org. Chem. 2016, 12, 2757–2762, doi:10.3762/bjoc.12.272

• ) to form benzyne or that organic electron donors form in situ with suitable additives under the basic conditions of the reaction [58][59][60]. For example, observation of faster direct arylation in the presence of DMF led to proposals of deprotonated DMF as one electron donor [61] or forming a dibasic

Towards the development of continuous, organocatalytic, and stereoselective reactions in deep eutectic solvents

• Davide Brenna,
• Elisabetta Massolo,
• Alessandra Puglisi,
• Sergio Rossi,
• Giuseppe Celentano,
• Maurizio Benaglia and
• Vito Capriati

Beilstein J. Org. Chem. 2016, 12, 2620–2626, doi:10.3762/bjoc.12.258

• reaction. The most explored strategies involve the development of a new class of catalysts (mainly prolinamide derivatives) [4][5][6], the study of additives in combination with proline itself [7][8][9][10][11][12][13], and the use of unusual reaction media [14][15][16][17][18][19]. In this context, it was

• stereochemistry of the intermediate species involved in the catalytic cycle [41]. The equilibrating nature of the aldol reaction and the influence of such reversibility on its stereochemical outcome has recently been studied [42]. It has also been reported that the use of additives may have a dramatic influence

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• separation. This yields much better performing devices, with improved curve shape, demonstrating the importance of morphology control in BHJ devices and improving the understanding of the role of solvent additives. Keywords: current voltage analysis; morphology; organic solar cells; Introduction Tremendous

• reduces the s-shape of the curve leading to a greatly enhanced FF. While the use of additives has been shown to have a number of consequences on film formation and device operation [38][39][40][41][42][43][44], to the best of our knowledge, such a dramatic change in curve shape has not been demonstrated

• previously using solvent additives. And while these additive-processed devices still have not nearly reached the full potential of this materials system, and other possible processing changes may also affect the nature of the J–V curve, we have focused herein on understanding the mechanism leading to the

The weight of flash chromatography: A tool to predict its mass intensity from thin-layer chromatography

• Freddy Pessel,
• Jacques Augé,
• Isabelle Billault and
• Marie-Christine Scherrmann

Beilstein J. Org. Chem. 2016, 12, 2351–2357, doi:10.3762/bjoc.12.228

• , but also the amount of non-reacting starting materials, auxiliaries, catalysts or any additives such as acids, bases, salts, solvents of the reaction or solvents required for the work-up and the purification. We demonstrated that the mass intensity could be easily calculated for linear and convergent

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• the last years especially as the parent alcohol of isosorbide. The latter is also a platform chemical with applications in pharmaceuticals, detergents, fuel additives, monomers and building blocks for new polymers and functional materials and new high boiling organic solvents. Conversion of D-sorbitol

Tunable microwave-assisted method for the solvent-free and catalyst-free peracetylation of natural products

• Manuela Oliverio,
• Paola Costanzo,
• Monica Nardi,
• Carla Calandruccio,
• Raffaele Salerno and
• Antonio Procopio

Beilstein J. Org. Chem. 2016, 12, 2222–2233, doi:10.3762/bjoc.12.214

• has been approved by the FDA (Food and Drug Administration). Even the EFSA (European Food Safety Agency) accepted peracetylation as a method to improve the solubility of natural ingredients in fatty matrix (peracetylated starches are labeled as E1420 in the Union list of Food Additives) [11

• attention to the final product safety, strictly connected to the consumers safety and health, push the pharmaceutical and food companies to prefer methods that allows to minimize the opportunity of the final product to get in touch with chemical additives. At the best of our knowledge, only few reports

Diels–Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels–Alder reaction

• Ángel Cantín,
• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2016, 12, 2181–2188, doi:10.3762/bjoc.12.208

• converted into a variety of liquid hydrocarbon fuels and fuel additives [11][12]. Catalysis is considered as one of the foundational pillars of green chemistry. Catalysis often reduces the energy requirements, permits the use of renewable feedstocks and less toxic reagents. Moreover, in most cases yields

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• collection. With the thermal stability of all-polymer and polymer-fullerene blend microstructures being particularly problematic [19], block copolymers present a potential solution. Indeed, it has been shown that when block copolymers are used as additives in bulk heterojunction donor–acceptor blend layers

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• transesterification reaction for the synthesis of organic carbonates Organic carbonates (OCs) are promising candidates as green replacements of conventional noxious solvents and fuel additives as well as for the development of innovative intermediates in the pharma, lubricant and polymer industries [55][56]. Before

• synthetic targets in view of the development of new greener solvents, additives, reagents, and in general of chemical products with improved safety and chemical properties. Structures of some representative SILs and PILs systems. MCF is a silica-based mesostructured material with ultra-large mesopores of 20

Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines

• David R. Chisholm,
• Garr-Layy Zhou,
• Ehmke Pohl,
• Roy Valentine and
• Andrew Whiting

Beilstein J. Org. Chem. 2016, 12, 1851–1862, doi:10.3762/bjoc.12.174

• , phosphine additives and strong heating or microwave conditions in order to effect coupling with most acetylenes. Accordingly, it was anticipated that the aryl iodides would be more versatile due to their greater propensity to undergo oxidative additions. Therefore, in this paper we report herein the

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

• Josef Schachtner,
• Patrick Bayer and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2016, 12, 1798–1811, doi:10.3762/bjoc.12.170

• possibly additives, the gas phase, containing the gaseous reagents, and the light (Figure 1). Only very few microreactor setups for such “quasi tri-phasic” processes have been reported [33][34]; most of them are film/falling film [22], microchannel [23][35] or simple tube reactors [35][36][37]. The reactor

• €. The wide variation of all three reaction components (liquid, gas, light) with regard to their nature (type of substrates, solvents, additives, gases, wavelength of light) and concentration (chemicals in solution, partial pressure of gas, light intensity) was a prime objective of this work. Furthermore

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• :PC71BM photoactive layer were also fabricated and tested. However, the PC71BM-based devices showed a slightly decreased performance compared to the PC61BM-based devices (Figure S5, Supporting Information File 1). Using additives or post-thermal annealing did not improve device performance. We speculate

TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals

• Mei-Yuan Hsu,
• Yi-Pei Liu,
• Sarah Lam,
• Su-Ching Lin and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2016, 12, 1758–1764, doi:10.3762/bjoc.12.164

• reaction conditions was tested and O-benzyl 2-deoxyglucoside 25 was produced in 59% yield in the presence of TMSBr (α:β = 3:1, Table 2, entry 1). To further improve the α-selectivity and the yield, various additives were screened (Table 2, entries 2–11) [73][74][75][76][77]. Several participating solvents

• of trisaccharide 66. Iterative synthesis of trisaccharide 66. Proposed mechanisms for TMSBr-mediated synthesis of 2-deoxyglycosides in the presence of TPPO. TMSBr-mediated thio-addition of glycals. Additives in TMSBr-mediated 2-deoxyglycosylation of glucal 1. TMSBr-mediated 2-deoxyglycosylation of

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications

• Desta Gedefaw,
• Marta Tessarolo,
• Margherita Bolognesi,
• Mario Prosa,
• Renee Kroon,
• Wenliu Zhuang,
• Patrik Henriksson,
• Kim Bini,
• Ergang Wang,
• Michele Muccini,
• Mirko Seri and
• Mats R. Andersson

Beilstein J. Org. Chem. 2016, 12, 1629–1637, doi:10.3762/bjoc.12.160

• spin-coated respectively from 1,2,4-trichlorobenzene (TCB) and 1,2-dichlorobenzene (ODCB) solutions (best solvents in terms of solubility and thin-film quality for each polymer) without the need of additional processing solvent additives. All the details for the fabrication and characterization of the

On the cause of low thermal stability of ethyl halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2016, 12, 1590–1597, doi:10.3762/bjoc.12.155

• acid was employed in all experiments. The temperature dependence in toluene-d8 as solvent was found to be similar in CD2Cl2 (Table 1, entries 11–13). Next, the effect of additives on the stability of the compounds was investigated. We first tested NEt3 (not shown), inspired by the prolonged lifetime of

Stereodynamic tetrahydrobiisoindole “NU-BIPHEP(O)”s: functionalization, rotational barriers and non-covalent interactions

• Golo Storch,
• Sebastian Pallmann,
• Frank Rominger and
• Oliver Trapp

Beilstein J. Org. Chem. 2016, 12, 1453–1458, doi:10.3762/bjoc.12.141

• long as their chirality can be controlled by chiral additives or auxiliaries. In addition, the simultaneous presence of both axially chiral BIPHEP enantiomers can be beneficial as this allows bidirectional control of enantioselectivity depending on temperature [14][15]. In this approach, both product

Molecular weight control in organochromium olefin polymerization catalysis by hemilabile ligand–metal interactions

• Stefan Mark,
• Hubert Wadepohl and
• Markus Enders

Beilstein J. Org. Chem. 2016, 12, 1372–1379, doi:10.3762/bjoc.12.131

• external donors (e.g., solvent molecules, substrates, additives, etc.) may displace a relatively strong intramolecular donor function. Several examples for olefin polymerization catalysts with hemilabile ligands are known and the impact of the hemilabile group on the polymerization behavior can be immense

Cyclisation mechanisms in the biosynthesis of ribosomally synthesised and post-translationally modified peptides

• Andrew W. Truman

Beilstein J. Org. Chem. 2016, 12, 1250–1268, doi:10.3762/bjoc.12.120

• without subsequent elimination. Wild-type NisB was then able to convert polyglutamylated NisA to dehydrated NisA without the need for any additives that are usually necessary for NisB in vitro activity, thus demonstrating that glutamylated NisA is an authentic activated intermediate. Subsequent

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

• Jakub Saadi,
• Christoph Bentz,
• Kai Redies,
• Dieter Lentz,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1236–1242, doi:10.3762/bjoc.12.118

• cyclization discussed in this report was discovered with cyclohexanone derivative 4 and we therefore tried to optimize the reaction conditions with this substrate. After extensive studies investigating different palladium catalysts, bases, additives, temperatures (with and without microwave) and reaction

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• chiral calcium alkoxide complex was generated in situ by mixing Ca(OEt)2, PyBox ligand (S,S)-88, and phenol 89. The authors found that the slow addition of malonate 86 and the use of phenol 89 and ethanol as additives were all crucial for achieving high yield and enantioselectivity, although the exact

Modular synthesis of the pyrimidine core of the manzacidins by divergent Tsuji–Trost coupling

• Sebastian Bretzke,
• Stephan Scheeff,
• Felicitas Vollmeyer,
• Friederike Eberhagen,
• Frank Rominger and
• Dirk Menche

Beilstein J. Org. Chem. 2016, 12, 1111–1121, doi:10.3762/bjoc.12.107

• additional additives to impede a possibly unfavorable amine coordination of the reactive ruthenium intermediates [51] did not improve the reaction outcome (entries 2–4). Following reports from Nolan and Prunet [52], as well as from Steinke and Vilar [53] we finally evaluated tricyclohexylphosphane oxides and

Iodine-mediated synthesis of 3-acylbenzothiadiazine 1,1-dioxides

• Long-Yi Xi,
• Ruo-Yi Zhang,
• Lei Shi,
• Shan-Yong Chen and
• Xiao-Qi Yu

Beilstein J. Org. Chem. 2016, 12, 1072–1078, doi:10.3762/bjoc.12.101

• % yield. To improve the yield of this product, a series of additives including acids, metal salt and bases were tested. However, to our disappointment, all of them could not promote this transformation (Table 1, entries 2–7). After optimizing the ratios of 1a and 2a, we found that increasing the amount of