From chemical metabolism to life: the origin of the genetic coding process

• Antoine Danchin

Beilstein J. Org. Chem. 2017, 13, 1119–1135, doi:10.3762/bjoc.13.111

• scenarios. To be sure, trying to understand the origins of life should be based on what we know of current chemistry in the solar system and beyond. There, amino acids and very small compounds such as carbon dioxide, dihydrogen or dinitrogen and their immediate derivatives are ubiquitous. Surface-based

• aromatic heterocycles) is based on the incorporation of amino acids in the core of nucleotide precursors. Pyrimidine nucleotide biosynthesis uses aspartate and combines together ubiquitous molecules, water, carbon dioxide, ammonium and phosphate (forming carbamoyl phosphate, also a precursor of arginine

The effect of cyclodextrin complexation on the solubility and photostability of nerolidol as pure compound and as main constituent of cabreuva essential oil

• Joyce Azzi,
• Pierre-Edouard Danjou,
• David Landy,
• Steven Ruellan,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2017, 13, 835–844, doi:10.3762/bjoc.13.84

• investigated by TOC analysis using a Shimadzu TOC-VCSH analyzer. It is based on the production of carbon dioxide (CO2) following oxidation of organic compounds. CO2 is then detected using a high-sensitivity infrared gas analyzer (NDIR). First, TOC was measured for the CD solution (TOCCD). Then, the amount of

Conjecture and hypothesis: The importance of reality checks

• David Deamer

Beilstein J. Org. Chem. 2017, 13, 620–624, doi:10.3762/bjoc.13.60

• chimney structures. The hydrogen gas dissolved in the alkaline vent fluid is a potential source of reducing power. Certain microorganisms already use hydrogen for this purpose, so the hydrothermal vent hypothesis proposes that on the prebiotic Earth hydrogen could potentially reduce carbon dioxide to

• vent conditions by injecting a solution of potassium phosphate, sodium silicate and sodium sulfide (pH 11) into a second solution of ferrous chloride, sodium bicarbonate and nickel chloride (pH 5). The aim was to determine whether carbon dioxide (present as 10 mM sodium bicarbonate) can be reduced

Adsorption of RNA on mineral surfaces and mineral precipitates

• Elisa Biondi,
• Yoshihiro Furukawa,
• Jun Kawai and
• Steven A. Benner

Beilstein J. Org. Chem. 2017, 13, 393–404, doi:10.3762/bjoc.13.42

• . These are interesting not only because carbon dioxide is likely to have been an abundant component of an early Earth atmosphere, but also because alkaline earths form a well-known set of binary carbonates that include insoluble magnesium, calcium, strontium, and barium carbonates (magnesite, calcite

Decarboxylative and dehydrative coupling of dienoic acids and pentadienyl alcohols to form 1,3,6,8-tetraenes

• Ghina’a I. Abu Deiab,
• Mohammed H. Al-Huniti,
• I. F. Dempsey Hyatt,
• Emma E. Nagy,
• Kristen E. Gettys,
• Sommayah S. Sayed,
• Christine M. Joliat,
• Paige E. Daniel,
• Rupa M. Vummalaneni,
• Andrew T. Morehead Jr,
• Andrew L. Sargent and
• Mitchell P. Croatt

Beilstein J. Org. Chem. 2017, 13, 384–392, doi:10.3762/bjoc.13.41

• accessible alcohol for a leaving group. This reaction was advanced to be possible in a two-component fashion, allowing for the conversion of dienoic acids and pentadienyl alcohols into 1,3,6,8-tetraenes with the only stoichiometric byproducts being water and carbon dioxide. These reactions currently require

Continuous N-alkylation reactions of amino alcohols using γ-Al₂O₃ and supercritical CO₂: unexpected formation of cyclic ureas and urethanes by reaction with CO₂

• Emilia S. Streng,
• Darren S. Lee,
• Michael W. George and
• Martyn Poliakoff

Beilstein J. Org. Chem. 2017, 13, 329–337, doi:10.3762/bjoc.13.36

• toxic solvents; furthermore post-reaction separation is simplified as the gas/liquid phases separate upon cooling. The use of supercritical methanol (scMeOH) for N-alkylation reactions has been reported before [29][30]. Our own investigations with heterogeneous catalysis in supercritical carbon dioxide

Diastereoselective anodic hetero- and homo-coupling of menthol-, 8-methylmenthol- and 8-phenylmenthol-2-alkylmalonates

• Matthias C. Letzel,
• Hans J. Schäfer and
• Roland Fröhlich

Beilstein J. Org. Chem. 2017, 13, 33–42, doi:10.3762/bjoc.13.5

• the benzyl ester 19 with lithium diisopropylamide and quenching the enolate with carbon dioxide (Scheme 2a). Benzyl 2-tert-butylmalonate (6) was prepared in good yield using a method of Krapcho et al. [18], by double deprotonation of 3,3-dimethylbutyric acid (20) with LDA and quenching the dianion

Catalytic Wittig and aza-Wittig reactions

• Zhiqi Lao and
• Patrick H. Toy

Beilstein J. Org. Chem. 2016, 12, 2577–2587, doi:10.3762/bjoc.12.253

• carbon dioxide (2 equivalents). While this reaction was described as being catalytic, the mass of the catalyst used was not explicitly reported, so it is impossible to determine the number of catalyst turnovers that were involved in generating the 20% isolated yield of 43. The authors only reported that

• ]. In this work, biaryl isocyanates 45 could be converted into phenanthridines 46, and aryl isocyanates 47 could be transformed into benzoxazoles 48 directly in refluxing toluene together with the simultaneous release of carbon dioxide. Presumably these reactions proceeded via iminophosphorane

A new paradigm for designing ring construction strategies for green organic synthesis: implications for the discovery of multicomponent reactions to build molecules containing a single ring

• John Andraos

Beilstein J. Org. Chem. 2016, 12, 2420–2442, doi:10.3762/bjoc.12.236

• either of carbon monoxide [141][142][143], carbon dioxide [144], dichloromethoxymethane [145][146], or methyl methylthiomethyl sulfoxide [147][148][149] as one-carbon fragments. The only literature example of a [4 + 2] strategy applied to cyclohexanone derivatives involved reaction of but-3-en-2-one with

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• Technology (KAIST), Guseong Dong, Yuseong Gu, Daejeon 305–701, Korea 10.3762/bjoc.12.220 Abstract Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• 10.3762/bjoc.12.185 Abstract Two hydroxy-functionalized hyper-cross-linked ultra-microporous compounds have been synthesized by Friedel–Crafts alkylation reaction and characterised with different spectroscopic techniques. Both compounds exhibit an efficient carbon dioxide uptake over other gases like N2

• , H2 and O2 at room temperature. A high isosteric heat of adsorption (Qst) has been obtained for both materials because of strong interactions between polar –OH groups and CO2 molecules. Keywords: carbon dioxide capture; hyper-cross-linked polymer; metal-organic framework; microporous organic polymer

• of hundred years in contrast to other greenhouse gases which leave the atmosphere with relatively smaller time scale [1]. The CO2 long life in the atmosphere provides the clearest possible rationale for carbon dioxide capture and storage. Previously, different types of amine solvents were employed to

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

• of oxygen and a palladium catalyst (Scheme 6, middle). Though safer than the phosgenation of methanol, these synthetic routes still involved poisonous carbon monoxide and methyl nitrite, and chlorine-based catalysts. Carbon dioxide is the natural green alternative carbonyl source to these undesirable

• feedstocks, in particular to CO, except that its thermodynamic stability poses severe challenges. This potential limitation was overcome by the Asahi Kasei Corp. that recently industrialized a catalytic polycarbonate production process based on the use of carbon dioxide (CO2) for the synthesis of DMC as an

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

• of luciferin yields the peroxy compound 1,2-dioxetane. This four-membered peroxide cycle is unstable and spontaneously decays to carbon dioxide and excited ketones, which release excess energy through light emission (bioluminescence) [62][63][64][65]. The in vivo oxidation of cholesterol by singlet

Methylpalladium complexes with pyrimidine-functionalized N-heterocyclic carbene ligands

• Dirk Meyer and
• Thomas Strassner

Beilstein J. Org. Chem. 2016, 12, 1557–1565, doi:10.3762/bjoc.12.150

• products while avoiding over-oxidation to carbon dioxide is still one of the most difficult tasks and considered to be one of the “Holy Grails” of chemistry [7]. Early work by Bergman [8][9] and Graham [10][11] showed that the activation of methane is possible, but their systems provided only

Recent advances in C(sp³)–H bond functionalization via metal–carbene insertions

• Bo Wang,
• Di Qiu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2016, 12, 796–804, doi:10.3762/bjoc.12.78

• impedes the use of most organic solvents, while the gaseous nature of methane makes it impossible to form a homogenous reaction system without a solvent. Pérez and co-workers addressed this problem by using supercritical carbon dioxide (scCO2) as the reaction medium. Methane can be dissolved in scCO2

• functionalization of the primary sites was observed in the presence of Tp(CF3)2,BrCu(MeCN); while hexane and scCO2 made little difference as compared to Tp(CF3)2,BrAg(thf) catalyzed reactions. These results may be related to the interaction of the ligand with carbon dioxide. A net electron density flux from the

• metal center to the ligand and to carbon dioxide was supported by experimental data and DFT studies. Such interaction increases the electrophilicity of the carbene moiety and thus lowers the activation energy for C–H bond insertion. Other ligands have also been explored for the metal–carbene C(sp3)–H

Opportunities and challenges for direct C–H functionalization of piperazines

• Zhishi Ye,
• Kristen E. Gettys and
• Mingji Dai

Beilstein J. Org. Chem. 2016, 12, 702–715, doi:10.3762/bjoc.12.70

• McDermott et al. in 2008 (Figure 6) [41]. In two steps (asymmetric deprotonation followed by a carbon dioxide quench and coupling with N-benzylpiperazine, 22) product 23 was produced in 48% yield with 89:11 enantioselectivity favoring the R-configuration of the newly generated carbon center. In contrast to

Highly stable and reusable immobilized formate dehydrogenases: Promising biocatalysts for in situ regeneration of NADH

• Barış Binay,
• Dilek Alagöz,
• Deniz Yildirim,
• Ayhan Çelik and
• S. Seyhan Tükel

Beilstein J. Org. Chem. 2016, 12, 271–277, doi:10.3762/bjoc.12.29

• decrease operational costs. NAD+-dependent formate dehydrogenase (FDH, EC 1.2.1.2) catalyzes oxidation of formate to carbon dioxide (CO2) [6]. FDH is industrially used as coenzyme for the regeneration of NADH [7][8], as sensor for the determination of formic acid [9], and as catalyst for the production 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

• hemiaminals derived from fluoral (CF3C(OSiMe3)NR2), can generate CnF2n+1Cu via carbon–carbon bond cleavage. Herein we focus on Cu-mediated perfluoroalkylation reactions through which carbon dioxide, the esters, or the N-formylamines are eliminated from the perfluoroalkyl reagents. Review Decarboxylation of

Convenient preparation of high molecular weight poly(dimethylsiloxane) using thermally latent NHC-catalysis: a structure-activity correlation

• Stefan Naumann,
• Johannes Klein,
• Dongren Wang and
• Michael R. Buchmeiser

Beilstein J. Org. Chem. 2015, 11, 2261–2266, doi:10.3762/bjoc.11.246

• -handle metal-free process which is more competitive in comparison with other catalytic systems can be realized [26]. Results and Discussion Several five-, six- and seven-membered NHCs were prepared and reacted with carbon dioxide to receive the corresponding CO2 adducts (Scheme 1, top), following

Robust bifunctional aluminium–salen catalysts for the preparation of cyclic carbonates from carbon dioxide and epoxides

• Yuri A. Rulev,
• Zalina Gugkaeva,
• Victor I. Maleev,
• Michael North and
• Yuri N. Belokon

Beilstein J. Org. Chem. 2015, 11, 1614–1623, doi:10.3762/bjoc.11.176

• one-component aluminium-based catalysts for the reaction between epoxides and carbon dioxide have been prepared. The catalysts are composed of aluminium–salen chloride complexes with trialkylammonium groups directly attached to the aromatic rings of the salen ligand. With terminal epoxides, the

• catalysts induced the formation of cyclic carbonates under mild reaction conditions (25–35 °C; 1–10 bar carbon dioxide pressure). However, with cyclohexene oxide under the same reaction conditions, the same catalysts induced the formation of polycarbonate. The catalysts could be recovered from the reaction

• mixture and reused. Keywords: aluminium; carbon dioxide; cyclic carbonate; epoxide; salen; Introduction Carbon dioxide is a renewable and inexpensive carbon source, so great efforts have been directed at developing novel methods for the valorization of this abundant raw material [1]. One way of

Surprisingly facile CO₂ insertion into cobalt alkoxide bonds: A theoretical investigation

• Willem K. Offermans,
• Claudia Bizzarri,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144

• Abstract Exploiting carbon dioxide as co-monomer with epoxides in the production of polycarbonates is economically highly attractive. More effective catalysts for this reaction are intensively being sought. To promote better understanding of the catalytic pathways, this study uses density functional theory

• , a linear Brønsted–Evans–Polanyi relationship was found between the activation energy and the reaction energy. Keywords: activation; alkoxide; carbon dioxide; cobalt; insertion; salen; Introduction Carbon dioxide (CO2) has been known to be an attractive carbon source for decades [1][2][3][4][5][6

• be very beneficial to harness a part of this stream for producing valuable products [7]. From a thermodynamic point of view, however, CO2 is highly stable and, thus, shows low reactivity. One way to overcome this thermodynamic hurdle is to react carbon dioxide with relatively high-energy molecules

The synthesis of active pharmaceutical ingredients (APIs) using continuous flow chemistry

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134

• intermediate passes into a tube-in-tube reactor, where carboxylation takes place furnishing the lithium carboxylate 129. Excess carbon dioxide is subsequently removed using a degassing tube before reacting species 129 with a further stream of n-BuLi to induce cyclisation to dibenzosuberone (130) in a short

Azobenzene-based inhibitors of human carbonic anhydrase II

• Leander Simon Runtsch,
• David Michael Barber,
• Peter Mayer,
• Michael Groll,
• Dirk Trauner and
• Johannes Broichhagen

Beilstein J. Org. Chem. 2015, 11, 1129–1135, doi:10.3762/bjoc.11.127

• kinetics. Keywords: azobenzene chemistry; enzyme inhibitors; human carbonic anhydrase II; sulfonamide; X-ray crystallography; Introduction Carbonic anhydrase (CA) is an ubiquitously found zinc-containing metalloenzyme with many isoforms, which all catalyze the conversion of carbon dioxide and water to

• hCAII. a) hCAII (pdb: 2vva [7]) catalyzes the hydration of carbon dioxide to bicarbonate and a proton (left) as well as the hydrolysis of pNPA to acetate and a colored phenolate (λmax = 400 nm). b) Aryl sulfonamide-containing pharmacophores of hCAII. c) Aryl sulfonamide merged to azobenzenes. Crystal

DBU-promoted carboxylative cyclization of o-hydroxy- and o-acetamidoacetophenone

• Wen-Zhen Zhang,
• Si Liu and
• Xiao-Bing Lu

Beilstein J. Org. Chem. 2015, 11, 906–912, doi:10.3762/bjoc.11.102

• Wen-Zhen Zhang Si Liu Xiao-Bing Lu State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, P. R. China 10.3762/bjoc.11.102 Abstract The carboxylative cyclization of o-hydroxy- and o-acetamidoacetophenone with carbon dioxide promoted by the organic base 1,8

• -diazabicycloundec-7-ene (DBU) is reported. This reaction provides convenient access to the biologically important compounds 4-hydroxy-2H-chromen-2-one and 4-hydroxy-2(1H)-quinolinone in moderate to good yields using carbon dioxide as the carboxylation reagent. An acyl migration from nitrogen to carbon is observed

• in the reaction of o-acetamidoacetophenone. Keywords: acyl migration; carbon dioxide; carboxylation; cyclization; condensation; Introduction 4-Hydroxy-2H-chromen-2-ones and 4-hydroxy-2(1H)-quinolinones are key structural subunits found in many natural products [1], commercial drugs [2][3] and

CO₂ Chemistry

• Thomas E. Müller and
• Walter Leitner

Beilstein J. Org. Chem. 2015, 11, 675–677, doi:10.3762/bjoc.11.76

• will continue to be carbon-based. One of the most abundant renewable resources of carbon is carbon dioxide (Figure 1). Carbon capture technologies are being implemented [1] to capture a part of the yearly anthropogenic CO2 emission of 36,600 million metric tons of CO2 [2]. If only a fraction of the

• use of carbon dioxide as chemical feedstock. Notably, the use of CO2 for manufacturing materials and chemicals is still in its infancy. Carbon dioxide (CO2) has long stirred the fascination of chemists. A rich chemistry has evolved utilizing this molecule in chemical synthesis [4]. Hitherto the low

• reactivity of the CO2 molecule poses significant challenges to the utilization of carbon dioxide in industrial applications. Thus, the CO2 molecule is commonly perceived to be highly inert. This perception clearly stems from the high chemical stability of carbon dioxide. However, the reactivity of the CO2