Vicinal difunctionalization of alkenes by four-component radical cascade reaction of xanthogenates, alkenes, CO, and sulfonyl oxime ethers

• Shuhei Sumino,
• Takahide Fukuyama,
• Mika Sasano,
• Ilhyong Ryu,
• Antoine Jacquet,
• Frédéric Robert and
• Yannick Landais

Beilstein J. Org. Chem. 2019, 15, 1822–1828, doi:10.3762/bjoc.15.176

• stirring bar, 1a (90.1 mg, 0.4 mmol), 2a (455.3 mg, 4.0 mmol), 3a (141.4 mg, 0.51 mmol), (Bu3Sn)2 (474.7 mg, 0.82 mmol), DTBHN (21.4 mg, 0.12 mmol), and 1,2-dichloroethane (8 mL) were placed in a stainless steel autoclave. The autoclave was closed, purged three times with carbon monoxide, pressurized with

• equipped with two sapphire glass windows and an inserted Pyrex glass liner. The autoclave was closed, purged three times with carbon monoxide, pressurized with 130 atm of CO and then irradiated by Xenon lamp (500 W) with stirring for 16 h. Excess CO was discharged after the reaction. The reaction mixture

Functional panchromatic BODIPY dyes with near-infrared absorption: design, synthesis, characterization and use in dye-sensitized solar cells

• Quentin Huaulmé,
• Cyril Aumaitre,
• Outi Vilhelmiina Kontkanen,
• David Beljonne,
• Alexandra Sutter,
• Gilles Ulrich,
• Renaud Demadrille and
• Nicolas Leclerc

Beilstein J. Org. Chem. 2019, 15, 1758–1768, doi:10.3762/bjoc.15.169

• [30]. The introduction of the aldehyde moiety is carried out through catalytic carbo-palladation reaction using molecular carbon monoxide in the presence of methyl formiate as hydrogen source in modest yield (35% and 19% for 8 and 10, respectively) due to the formation of a relatively large amount of

• %, 6: 30%; d) (3-(2-methoxyethoxy)prop-1-yn-1-yl)magnesium bromide, THF, 60 °C, 85%; e) carbon monoxide, sodium formiate, [Pd(PPh3)2Cl2], anhydrous DMF, 100 °C, 8: 19%, 9: 35%; f) cyanoacetic acid, piperidine, MeCN, CHCl3, 80 °C, BOD-TTPA: 34%, BOD-TTPA-alk: 26%. a) Absorption spectra of compounds BOD

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• , leading to final lactams 20. This mechanism is partially corroborated by the following multicomponent synthesis where benzamide 21, ortho-functionalized with a terminal alkyne group (Scheme 5), a secondary amine 22 and carbon monoxide (23) react to produce 3-methyleneisoindolinones 24 [80]. A palladium

• , 2-bromobenzaldehydes 62 and carbon monoxide (23) at atmospheric pressure, with the assistance of DABCO as base and tri(tert-butyl)phosphonium tetrafluoroborate as ligand (Scheme 19) [100]. A variety of substituents in the benzene rings (R1, R3) are compatible with the reaction conditions, but

• three-component reaction between aryl iodides, incorporating a Michael acceptor 105, amines and amides 2 and carbon monoxide (23) (Scheme 30) [108]. It is remarkable that not only aromatic but also aliphatic amines and even amides and sulfonamides can be used as the nitrogen-containing substrate. With

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

• Yue Zhong,
• Wen-Yu Wu,
• Shao-Peng Yu,
• Tian-Yuan Fan,
• Hai-Tao Yu,
• Nian-Guang Li,
• Zhi-Hao Shi,
• Yu-Ping Tang and
• Jin-Ao Duan

Beilstein J. Org. Chem. 2019, 15, 291–298, doi:10.3762/bjoc.15.26

• compound C with a five-membered palladacycle. C undergoes the process of oxidative addition with ortho-bromobenzoyl chloride to give the PdIV intermediate D, and E can be obtained via a reductive elimination reaction. A novel aryl-PdII species F is formed through removing carbon monoxide from E. Ultimately

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

• Eric Detmar,
• Valentin Müller,
• Daniel Zell,
• Lutz Ackermann and
• Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545, doi:10.3762/bjoc.14.130

• . Selected intermediates and transition states are shown in Figure 2. The computational analysis starts with the catalytically active cobalt(III) acetate complex 4 which is generated in situ from the precatalyst [Cp*CoI2(CO)], AgSbF6, and KOAc. While the iodine ions are captured by Ag+, carbon monoxide

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

• Carmen Moreno-Marrodan,
• Francesca Liguori and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2017, 13, 734–754, doi:10.3762/bjoc.13.73

• more usual strategy is the so-called “selective poisoning”, i.e., the improvement of the catalyst’s selectivity by the addition of variable, often large, amount of contaminants, either organic ligands (quinolone [65][66], phosphine [67]), carbon monoxide [68], sulfides [69], sulfoxides [70][71] defined

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• the carbonylative cyclization reaction of carboxylic acid methyl and ethyl esters 42 which led to the formation of 1-indanones 43 [33]. This reaction was carried out in acetonitrile, in the presence of triethylamine, under carbon monoxide atmosphere, achieving efficiency in the range of 88–92%, when

Biochemical and structural characterisation of the second oxidative crosslinking step during the biosynthesis of the glycopeptide antibiotic A47934

• Veronika Ulrich,
• Clara Brieke and
• Max J. Cryle

Beilstein J. Org. Chem. 2016, 12, 2849–2864, doi:10.3762/bjoc.12.284

• of sodium dithionite led to conversion of ferric to ferrous heme, which was accompanied by shift of the Soret maximum to λ = 422 nm and of the β/α bands to λ = 532 and 559 nm in the UV–visible spectrum. Upon saturation of ferrous StaF with carbon monoxide, two major peaks appeared at λ = 420 and 450

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

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

• in terms of environmental impact, safety and economics. Thus, by the end of the 1990’s, two main phosgene-free large-capacity processes were operative, both based on the incorporation of carbon monoxide (CO) and methanol by transition metal catalysis: one developed by EniChem [57][58], and the other

• by Ube Industries [59]. The EniChem process involved an oxidative carbonylation of methanol, i.e., the reaction of methanol with carbon monoxide and oxygen catalyzed by cuprous chloride, while the Ube process used an oxidative carbonylation of methanol via methyl nitrite using NOx as oxidant, instead

• 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

Flow carbonylation of sterically hindered ortho-substituted iodoarenes

• Carl J. Mallia,
• Gary C. Walter and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2016, 12, 1503–1511, doi:10.3762/bjoc.12.147

• synthesis of ortho-substituted carboxylic acids, using carbon monoxide gas, has been studied for a number of substrates. The optimised conditions make use of a simple catalyst system compromising of triphenylphosphine as the ligand and palladium acetate as the pre-catalyst. Carbon monoxide was introduced

• via a reverse “tube-in-tube” flow reactor at elevated pressures to give yields of carboxylated products that are much higher than those obtained under normal batch conditions. Keywords: carbon monoxide; carbonylation of ortho-substituted substrates; flow chemistry; gases in flow; “tube-in-tube

• (Peflacine™). The low catalyst turnover frequency (T.O.F.) and poor yields associated with ortho-substituted transformations are attributed to the carbon monoxide coordination to the intermediate aryl transition metal (i.e., Pd) complex which is inhibited by sterics [15]. Following oxidative addition of the

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• multicomponent reactions Transition metals, especially Pd and Cu, are well-known catalysts for multicomponent reactions. Carbopalladation reactions of allenes, alkynes and carbon monoxide are very important processes in multicomponent syntheses. Additionally, copper-catalyzed multicomponent reactions such as

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

• -functionalization reaction of N-(2-pyridinyl)piperazines with carbon monoxide and terminal olefins (Figure 13) [52]. Their previous work on pyridinyl group-directed Rh-catalyzed carbonylation at sp3 C–H bonds adjacent to the nitrogen atom in other alkylamines such as pyrrolidine, piperidine, and

• tetrahydroisoquinoline [53][54] gave the carbonylation product directly. However, when piperazine substrates were used, an additional formal dehydrogenation process took place before the carbonylation reaction. As shown in Figure 13, under the conditions of 15 atm of carbon monoxide and ethylene, Rh4(CO)12 catalyst, and

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

• Carmen Mejuto,
• Beatriz Royo,
• Gregorio Guisado-Barrios and
• Eduardo Peris

Beilstein J. Org. Chem. 2015, 11, 2584–2590, doi:10.3762/bjoc.11.278

• complex described so far. To further evaluate the electron-donating character of the tris-MIC ligand B, the iridium hexacarbonyl complex 5 was obtained by bubbling carbon monoxide into a solution of 3 in CH2Cl2. The resulting yellow solid was obtained in 93% yield. The IR spectrum of a CH2Cl2 solution of

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

• Paul P. Kelly,
• Anja Eichler,
• Susanne Herter,
• David C. Kranz,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2015, 11, 1713–1720, doi:10.3762/bjoc.11.186

• expression levels in the respective sub-pools (Tables S2–S8, Supporting Information File 1). Screening for P450 expression The levels in P450 expression were determined using CO difference spectroscopy in whole cells. The assay could be significantly improved both in terms of speed and safety by using carbon

• monoxide releasing molecules (CORMs) [35][36][37] as a source of CO rather than the gas CO itself. P450 concentrations determined in whole cells (1.1–5.9 µM) incubated with CORMs were similar or slightly higher when compared to concentrations determined in cell-free extracts (1.1–4.9 µM) treated with

A catalyst-free multicomponent domino sequence for the diastereoselective synthesis of (E)-3-[2-arylcarbonyl-3-(arylamino)allyl]chromen-4-ones

• Pitchaimani Prasanna,
• Pethaiah Gunasekaran,
• Subbu Perumal and
• J. Carlos Menéndez

Beilstein J. Org. Chem. 2014, 10, 459–465, doi:10.3762/bjoc.10.43

• –Hilman condensation, and a final deoxygenation. The deoxygenation is assumed to be induced by carbon monoxide resulting from the thermal decomposition of the dimethylformamide solvent. Keywords: chromones; domino reactions; Michael additions; multicomponent reactions; transfer hydrogenation

• tautomeric equilibrium. However, this reaction failed to show any incorporation of deuterium into 5, and therefore we had to abandon the hydride-transfer hypothesis. We came up with an alternative explanation based on the well-known fact that DMF decomposes into dimethylamine and carbon monoxide at its

• boiling point. Carbon monoxide can act as a deoxygenating agent [62] and thus explain the transformation of 6 into 5 as shown in Scheme 4. Because of the synthetic interest of allylic and benzylic deoxygenations, further research into this reaction is under way in our laboratories. Conclusion We have

One-pot synthesis of cyanohydrin derivatives from alkyl bromides via incorporation of two one-carbon components by consecutive radical/ionic reactions

• Shuhei Sumino,
• Akira Fusano,
• Hiroyuki Okai,
• Takahide Fukuyama and
• Ilhyong Ryu

Beilstein J. Org. Chem. 2014, 10, 150–154, doi:10.3762/bjoc.10.12

• bromides and nucleophilic addition of a cyanide ion was investigated, which gave moderate to good yields of cyanohydrin derivatives in one-pot. Keywords: alkyl bromide; carbon monoxide; cyanohydrin; ethyl cyanoformate; multicomponent; radical reaction; Introduction Radical carbonylation reactions have

Thermochemistry and photochemistry of spiroketals derived from indan-2-one: Stepwise processes versus coarctate fragmentations

• Götz Bucher,
• Gernot Heitmann and
• Rainer Herges

Beilstein J. Org. Chem. 2013, 9, 1668–1676, doi:10.3762/bjoc.9.191

• spectroscopy. Unfortunately no product could be unambiguously identified. The FVP of 2 yielded the product spectrum shown in Figure 5. Again, both carbon monoxide and carbon dioxide were formed along with the organic products. Carbon monoxide was formed in large excess over carbon dioxide (CO/CO2 = 13.5:1

• spiroketal linkage. The relative ratio of carbon dioxide and carbon monoxide being formed (CO2/CO = 1:27) indicates that a coarctate fragmentation of 1 can play a minor role only, if any. The composition of the product mixture is best rationalized by a series of stepwise processes, which starts with either a

A construction of 4,4-spirocyclic γ-lactams by tandem radical cyclization with carbon monoxide

• Mitsuhiro Ueda,
• Yoshitaka Uenoyama,
• Nozomi Terasoma,
• Shoko Doi,
• Shoji Kobayashi,
• Ilhyong Ryu and
• John A. Murphy

Beilstein J. Org. Chem. 2013, 9, 1340–1345, doi:10.3762/bjoc.9.151

• azides with CO was achieved. The reaction of iodoaryl allyl azides, TTMSS and AIBN under CO pressure (80 atm) in THF at 80 °C gave the desired 4,4-spirocyclic indoline, benzofuran, and oxindole γ-lactams in moderate to good yields. Keywords: 4,4-spirocyclic indol γ-lactams; carbon monoxide; free radical

Flow photochemistry: Old light through new windows

• Jonathan P. Knowles,
• Luke D. Elliott and
• Kevin I. Booker-Milburn

Beilstein J. Org. Chem. 2012, 8, 2025–2052, doi:10.3762/bjoc.8.229

• oxidation of both carbon monoxide and methanol has been followed in a microreactor through the use of quadrupole mass spectrometry (QMS). The levels of time resolution and versatility of detection offered by this method were reported to be far better than that available from conventional GC analysis and

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

Palladium-catalyzed dual C–H or N–H functionalization of unfunctionalized indole derivatives with alkenes and arenes

• Gianluigi Broggini,
• Egle M. Beccalli,
• Andrea Fasana and
• Silvia Gazzola

Beilstein J. Org. Chem. 2012, 8, 1730–1746, doi:10.3762/bjoc.8.198

• , exploiting the nucleophilicity of the C-2 and C-3 indolyl positions and the subsequent addition of carbon monoxide and the proper alcohol, a broad range of alkoxycarbonyl-substituted indoles fused to various sizes of rings has been achieved under mild conditions. A similar intermolecular version of the

• . The subsequent transfer of carbon monoxide with stereochemical retention determines the generation of the σ-acyl-palladium complex XVIII, which in turn is converted in the final cis-substituted tetrahydrocarbazole by methanolysis giving the carboxylation step. Again, the released Pd(0) species

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• , thioether and ester groups, although enolizable alkylimines were not suitable under these conditions (Scheme 1). Replacement of the acid chloride with a chloroformate under 1 atmosphere of carbon monoxide as a fourth component led to ketocarbamates 3 in a single operation through a carbonylative coupling [3

• , based on a similar strategy, through the assembly of four components, namely, imines, acid chloride and carbon monoxide. The process is thought to begin with formation of a münchnone 5, resulting from oxidative addition of an acyliminium species to Pd(0), followed by CO insertion and β-hydride

• different approach to α,β-alkynyl ketone derivatives as pyrazole precursors. They established a four-component domino process combining various organic halides, terminal alkynes, hydrazines, and carbon monoxide at room temperature. In this case, all components are mixed at the very beginning of the process

Koch–Haaf reaction of adamantanols in an acid-tolerant hastelloy-made microreactor

• Takahide Fukuyama,
• Yu Mukai and
• Ilhyong Ryu

Beilstein J. Org. Chem. 2011, 7, 1288–1293, doi:10.3762/bjoc.7.149

• practical organic syntheses using flow microreactors, and we have reported thus far examples of Pd-catalyzed coupling reactions [11][12][13], radical reactions [14][15][16], and photoreactions [17][18][19][20][21]. Carbonylation reactions are a powerful tool for the introduction of carbon monoxide into