The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

Organic chemistry on surfaces: Direct cyclopropanation by dihalocarbene addition to vinyl terminated self-assembled monolayers (SAMs)

• Malgorzata Adamkiewicz,
• David O’Hagan and
• Georg Hähner

Beilstein J. Org. Chem. 2014, 10, 2897–2902, doi:10.3762/bjoc.10.307

• reported the formation of high quality vinyl-terminated SAMs generated from the vapour phase by adsorption of octadecyltrichlorosilanes onto silicon wafers [16]. With access to these SAMs it became an objective to explore functional group modification of the vinyl double bond. Carbon–carbon bond formation

A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

• Claudia A. Contreras-Celedón,
• Darío Mendoza-Rayo,
• José A. Rincón-Medina and
• Luis Chacón-García

Beilstein J. Org. Chem. 2014, 10, 2821–2826, doi:10.3762/bjoc.10.299

• are tolerated. Keywords: 4-aminoantipyrine; arylboronic acids; biaryls; cross-coupling; palladium(II) complex; Introduction The sp2–sp2 carbon–carbon bond formation through cross-coupling reactions catalyzed by metal complexes has emerged as a powerful tool in organic synthesis [1][2][3][4][5][6

One-pot four-component reaction for convenient synthesis of functionalized 1-benzamidospiro[indoline-3,4'-pyridines]

• Chao Wang,
• Yan-Hong Jiang and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2014, 10, 2671–2676, doi:10.3762/bjoc.10.281

• situ formed Huisgen’s 1,4-dipoles were subsequently entrapped by various electrophiles and other reagents to finish a number of carbon–carbon bond formation reactions and heterocyclic construction processes [16][17][18]. A literature survey indicated that the common nitrogen-containing nucleophiles for

Organic synthesis using photoredox catalysis

• Axel G. Griesbeck

Beilstein J. Org. Chem. 2014, 10, 1097–1098, doi:10.3762/bjoc.10.107

• -coated semiconductor nanoparticles. On the substrate side, the focus is on redox-active donor/acceptor molecules, which range from all kind of aromatic, olefinic and carbonyl-type electron acceptor compounds to heteroatom-linked electron donors. The relevance of carbon–carbon bond formation for organic

Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

• Phei Li Lau,
• Ray W. K. Allen and
• Peter Styring

Beilstein J. Org. Chem. 2013, 9, 2886–2897, doi:10.3762/bjoc.9.325

• ; flow chemistry; Heck; palladium; supercritical carbon dioxide; Introduction The use of cross-coupling reactions between organometallic reagents and organic halides as a straightforward method of carbon–carbon bond formation has gained much popularity over the past three decades. The development of

Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

• Sudipta Pathak,
• Kamalesh Debnath and
• Animesh Pramanik

Beilstein J. Org. Chem. 2013, 9, 2344–2353, doi:10.3762/bjoc.9.269

• easily synthesized from silica gel and chlorosulfonic acid [26], was observed to improve the reactivity and selectivity in carbon–carbon bond-formation reactions [27][28], in cycloaddition reactions [29][30], in protection–deprotection reactions of multistep syntheses [31][32][33], in esterifications [34

Regioselective carbon–carbon bond formation of 5,5,5-trifluoro-1-phenylpent-3-en-1-yne

• Motoki Naka,
• Tomoko Kawasaki-Takasuka and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2013, 9, 2182–2188, doi:10.3762/bjoc.9.256

• Motoki Naka Tomoko Kawasaki-Takasuka Takashi Yamazaki Division of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16, Nakamachi, Koganei 184-8588, Japan 10.3762/bjoc.9.256 Abstract The regioselective carbon–carbon bond formation was studied

Cascade radical reaction of substrates with a carbon–carbon triple bond as a radical acceptor

• Hideto Miyabe,
• Ryuta Asada and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2013, 9, 1148–1155, doi:10.3762/bjoc.9.128

• chemistry has been developed as one of the most powerful tools for carbon–carbon bond formation in organic synthesis [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Particularly, the advantages for utilizing the radical methodologies are the high functional group tolerance and the

C–C Bond formation catalyzed by natural gelatin and collagen proteins

• Dennis Kühbeck,
• Basab Bijayi Dhar,
• Eva-Maria Schön,
• Carlos Cativiela,
• Vicente Gotor-Fernández and
• David Díaz Díaz

Beilstein J. Org. Chem. 2013, 9, 1111–1118, doi:10.3762/bjoc.9.123

• implications from a metabolic perspective. Keywords: biocatalysis; carbon–carbon bond formation; gelatin; Henry reaction; protein; Introduction Gelatin is a mixture of hot-water-soluble proteins of high average molecular weights (50–100 kDa) derived primarily from collagen, which is the main naturally

Synthesis of functionalized spiro[indoline-3,4’-pyridines] and spiro[indoline-3,4’-pyridinones] via one-pot four-component reactions

• Li-Juan Zhang,
• Qun Wu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2013, 9, 846–851, doi:10.3762/bjoc.9.97

• arylamines and other primary amines. Keywords: 1,4-dihydropyridine; electron-deficient alkyne; four-component reaction; isatin; one-pot reaction; spiro compound; Introduction β-Enaminones and β-enamino esters represent important synthetic building blocks for the development of versatile carbon–carbon bond

• -formation reactions and heterocyclic constructions [1][2][3][4][5]. In recent years, the in situ generated β-enamino esters, which could be easily obtained from the addition of aliphatic or aromatic primary amines to the activated alkynes, have been widely recognized as practical synthons for the synthesis

Some aspects of radical chemistry in the assembly of complex molecular architectures

• Béatrice Quiclet-Sire and
• Samir Z. Zard

Beilstein J. Org. Chem. 2013, 9, 557–576, doi:10.3762/bjoc.9.61

• assembly of complex molecular scaffolds. The emphasis is placed on the use of nitrogen-centred radicals, on the degenerate addition–transfer of xanthates, especially on its potential for intermolecular carbon–carbon bond formation, and on the generation and capture of radicals through electron transfer

• the allylation procedure with the simplest vinyl epoxide to furnish derivative 148. It is interesting to note that the carbon–carbon bond formation takes place in ketoester xanthate 146 on the carbon bearing the least acidic hydrogens. Triethylborane, through its autoxidation, serves to initiate the

• degenerative radical addition–transfer of xanthates is by far the most powerful radical chemistry that we have been able to discover, for it allows efficient intermolecular carbon–carbon bond formation starting with unactivated alkenes under very mild experimental conditions. Various functional groups can

Easy and direct conversion of tosylates and mesylates into nitroalkanes

• Alessandro Palmieri,
• Serena Gabrielli and
• Roberto Ballini

Beilstein J. Org. Chem. 2013, 9, 533–536, doi:10.3762/bjoc.9.58

• electron-withdrawing effect of the nitro group, nitroalkanes are prone to afford, under basic conditions, stabilized carbanions, which are commonly used as nucleophiles with a variety of electrophiles [8][9][10][11] leading to carbon–carbon bond formation. Furthermore, by making use of the possibility to

Inter- and intramolecular enantioselective carbolithiation reactions

• Asier Gómez-SanJuan,
• Nuria Sotomayor and
• Esther Lete

Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36

• . In this case, the use of a copper-base chiral catalytic system allows carbon–carbon bond formation by allylic alkylation with alkyllithiums, with high enantioselectivities and high functional-group tolerance [28][29]. This process may open new interesting applications in organolithium chemistry

Organocatalytic asymmetric addition of malonates to unsaturated 1,4-diketones

• Sergei Žari,
• Tiiu Kailas,
• Marina Kudrjashova,
• Mario Öeren,
• Ivar Järving,
• Toomas Tamm,
• Margus Lopp and
• Tõnis Kanger

Beilstein J. Org. Chem. 2012, 8, 1452–1457, doi:10.3762/bjoc.8.165

• enantioenriched products through a carbon–carbon bond formation [1][2][3][4][5]. Recently, unsaturated 1,4-dicarbonyl compounds, such as 1,4-ketoesters [6][7][8], 1,4-diketones [9], 1,4-ketoamides [9][10] and dialkylfumarates [11], have been the substrates for this reaction. The reaction products can undergo

Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

• Stefan Bräse,
• Nicole Volz,
• Franziska Gläser and
• Martin Nieger

Beilstein J. Org. Chem. 2012, 8, 1385–1392, doi:10.3762/bjoc.8.160

• synthesis. Keywords: cannabinoids; Diels–Alder reaction; natural product synthesis; organocatalysis; Introduction The Diels–Alder reaction is one of the most important processes for carbon–carbon-bond formation in organic chemistry [1][2]. Especially in the synthesis of natural products it is a widely

The Eschenmoser coupling reaction under continuous-flow conditions

• Sukhdeep Singh,
• J. Michael Köhler,
• Andreas Schober and
• G. Alexander Groß

Beilstein J. Org. Chem. 2011, 7, 1164–1172, doi:10.3762/bjoc.7.135

• blocks as shown in Scheme 1. Due to the ease of accessibility of the building blocks and the usually high-yielding S-alkylation step, the Eschenmoser coupling is an interesting reaction for diversity-oriented combinatorial synthesis [15][16][17]. The new carbon–carbon bond formation occurs during the

When gold can do what iodine cannot do: A critical comparison

• Sara Hummel and
• Stefan F. Kirsch

Beilstein J. Org. Chem. 2011, 7, 847–859, doi:10.3762/bjoc.7.97

• determined by the stability of the intermediate upon carbon–carbon bond formation. It was found that the substitution pattern of the alkene moiety influenced the cyclization mode, whereby a substituent at C2 encourages 6-exo cyclization, and a disubstituted C1 favors 5-exo cyclization. On the other hand

Asymmetric synthesis of tertiary thiols and thioethers

• Jonathan Clayden and
• Paul MacLellan

Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68

• alkene towards attack by the sulfur nucleophile. 2 Carbon–carbon bond formation 2.1 Electrophilic addition to α-thioenolates Diastereoselective alkylation of α-thioenolates has been used to prepare several types of enantiomerically pure tertiary thioethers [49][50][51][52][53][54]. The method of “self

• thiocarbamates Carbon–carbon bond formation in configurationally stable α-thioorganolithiums allows access to non-racemic tertiary thiols of varying structure and complexity. Hoppe’s extensive studies of lithiated thiocarbamates have continued to display the synthetic utility of these species in the formation of

Palladium-catalyzed formation of oxazolidinones from biscarbamates: a mechanistic study

• Benan Kilbas and
• Metin Balci

Beilstein J. Org. Chem. 2011, 7, 246–253, doi:10.3762/bjoc.7.33

• nucleophile is not necessary to form oxazolidinones. The metal is probably bonded to the allylic system from the same face as the nucleophile. Keywords: bicyclic endoperoxides; biscarbamates; oxazolidinone; Pd-catalyzed allylic reaction; singlet oxygen; Introduction Palladium-catalyzed carbon–carbon bond

• formation reactions in synthetic organic chemistry have attracted considerable attention in recent years [1]. Palladium-catalyzed allylation is also a particularly useful method for the activation of allylic substrates [2]. Trost et al. described a highly stereoselective synthesis of oxazolidinone 2

Olefin metathesis in nano-sized systems

• Didier Astruc,
• Abdou K. Diallo,
• Sylvain Gatard,
• Liyuan Liang,
• Cátia Ornelas,
• Victor Martinez,
• Denise Méry and
• Jaime Ruiz

Beilstein J. Org. Chem. 2011, 7, 94–103, doi:10.3762/bjoc.7.13

• -cored stars. Multiple carbon–carbon bond formation upon RCM and CM, and the complete switch of selectivity in the presence of acrylic acid. Example of chemo-, regio- and stereoselective CM of polyolefin dendrimers catalyzed by the 2nd generation Grubbs metathesis catalyst to produce water-soluble

Pd-catalyzed decarboxylative Heck vinylation of 2-nitrobenzoates in the presence of CuF₂

• Lukas J. Gooßen,
• Bettina Zimmermann and
• Thomas Knauber

Beilstein J. Org. Chem. 2010, 6, No. 43, doi:10.3762/bjoc.6.43

• applicable reactions for carbon–carbon bond formation in organic synthesis. Over the last decade, several highly active catalyst systems have been developed for these reactions [4][5]. Usually, aryl halides are employed as starting materials [6][7][8][9], but other aryl sources such as aryl triflates [10][11

Diastereoselective functionalisation of benzo-annulated bicyclic sultams: Application for the synthesis of cis-2,4-diarylpyrrolidines

• Susan Kelleher,
• Pierre-Yves Quesne and
• Paul Evans

Beilstein J. Org. Chem. 2009, 5, No. 69, doi:10.3762/bjoc.5.69

• -disubstituted pyrrolidine. In this sequence, the sulfonyl moiety not only serves as an amino protecting group but also facilitates the diastereoselective intramolecular carbon–carbon bond formation. In this present study we demonstrate that this general concept may be extended enabling the diastereoselective

A convenient allylsilane- N-acyliminium route toward indolizidine and quinolizidine alkaloids

• Roland Remuson

Beilstein J. Org. Chem. 2007, 3, No. 32, doi:10.1186/1860-5397-3-32

• ] The allylsilyl functional group is a weak carbon nucleophile for trapping N-acyliminium ions, thus providing a useful method for intramolecular carbon-carbon bond formation. [28][29] We have applied this methodology towards the synthesis of indolizidine alkaloids. (vide supra) We describe here a new