Copper-mediated arylation with arylboronic acids: Facile and modular synthesis of triarylmethanes

• H. Surya Prakash Rao and
• A. Veera Bhadra Rao

Beilstein J. Org. Chem. 2016, 12, 496–504, doi:10.3762/bjoc.12.49

• [1][2][3][4]. Although the group can be restricted to such molecules, many closely related derivatives that have a triarylmethane motif (like those having a heteroatom attached to the central carbon atom or the central carbon is sp2 hybridized) have been included in this class [5]. Molecules with a

Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes

• Adrián Gómez-Suárez,
• Yoshihiro Oonishi,
• Anthony R. Martin and
• Steven P. Nolan

Beilstein J. Org. Chem. 2016, 12, 172–178, doi:10.3762/bjoc.12.19

• , the selectivity dropped dramatically and a 1:0.43 ratio of products was observed (3nt, Scheme 5). In order to further test our hypothesis, the polarization of the alkyne was next reduced, but the potential chelating heteroatom was retained. The hydrophenoxylation of the unsymmetrical propargylic ether

Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

• Diego M. Andrada,
• Nicole Holzmann,
• Thomas Hamadi and
• Gernot Frenking

Beilstein J. Org. Chem. 2015, 11, 2727–2736, doi:10.3762/bjoc.11.294

• Ccarb−X bonds. The NBO data indicate that the occupation of the p(π) AO of the Ccarb atom is between 0.81 e (8, and 9) and 0.49 e (6). The p(π) occupation at the Ccarb atom is particularly large for the carbenes which have no heteroatoms bonded to it (9, and 14) or only one heteroatom as in 8. The

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• -catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the

• construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds. Keywords: asymmetric; carbon–heteroatom bond; copper; coupling; Introduction Copper-mediated coupling

• reactions to be carried out under much milder conditions. In the meantime these reactions have become one of the most classic, efficient and powerful methods for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds. Extensive applications have been developed in both academia and industry [6][7

Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

• Thibault E. Schmid,
• Sammy Drissi-Amraoui,
• Christophe Crévisy,
• Olivier Baslé and
• Marc Mauduit

Beilstein J. Org. Chem. 2015, 11, 2418–2434, doi:10.3762/bjoc.11.263

• ; sequential addition; Introduction Amongst the variety of synthetic methods available for the formation of C–C or C–heteroatom bonds, the asymmetric conjugate addition (ACA) of nucleophiles to electron-deficient alkenes is one of the most relevant and versatile for the synthesis of complex chiral molecules

Co-solvation effect on the binding mode of the α-mangostin/β-cyclodextrin inclusion complex

• Chompoonut Rungnim,
• Sarunya Phunpee,
• Manaschai Kunaseth,
• Supawadee Namuangruk,
• Kanin Rungsardthong,
• Thanyada Rungrotmongkol and
• Uracha Ruktanonchai

Beilstein J. Org. Chem. 2015, 11, 2306–2317, doi:10.3762/bjoc.11.251

• around the α-MGS in the formed inclusion complexes. The gij(r) was calculated as a function of the ethanol or water oxygen atom j within a spherical radius of r from the α-MGS heteroatom (oxygen atom i). The RDF results of ethanol and water co-solvation are shown in the left and right columns of Figure 6

Molecular-oxygen-promoted Cu-catalyzed oxidative direct amidation of nonactivated carboxylic acids with azoles

• Wen Ding,
• Shaoyu Mai and
• Qiuling Song

Beilstein J. Org. Chem. 2015, 11, 2158–2165, doi:10.3762/bjoc.11.233

• [25][26]. Currently, copper-catalyzed, aerobic, oxidative transformations with dioxygen as the sole oxidant have emerged as a useful and powerful strategy to construct carbon–carbon and carbon–heteroatom bonds [27][28][29]. It is known that Cu(II) superoxide species are usually reported to be formed

Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

• Cesar Garcias-Morales,
• David Ortegón-Reyna and
• Armando Ariza-Castolo

Beilstein J. Org. Chem. 2015, 11, 1973–1984, doi:10.3762/bjoc.11.213

• hyperconjugation, which is related to the anomeric effect (effect where a heteroatomic substituent adjacent to a heteroatom within a cyclohexane ring prefers the axial orientation instead of the equatorial) [6][7][8][9][10][11][12]. Moreover, stereoelectronic effects have been related to the stabilization of

• heteroatom, this is known as homoanomeric effect, which is a type of homohyperconjugation [28][29][30][31][32][33][34][35][36]. The homoanomeric effect can be observed in two cases: the first-one through a W-arrangement, where the lone-pair electrons (LPEs) of O, N, and S, on the pseudo equatorial position

New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP

• Patrycja Żak,
• Szymon Rogalski,
• Mariusz Majchrzak,
• Maciej Kubicki and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2015, 11, 1910–1916, doi:10.3762/bjoc.11.206

• . Coordination motif of latent catalyst of olefin metathesis in which alkylidene ligand is bound to the heteroatom X, acting as an anionic ligand. Known latent catalysts of olefin metathesis in which alkylidene ligands are bound to a heteroatom, acting as an anionic ligand. Selected, known aryloxybenzylidene

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

• Albert Poater and
• Luigi Cavallo

Beilstein J. Org. Chem. 2015, 11, 1767–1780, doi:10.3762/bjoc.11.192

• field for the synthesis of C–C double bonds [7][8][9]. After the discovery of well-defined Ru-based (pre)catalysts, such as (PCy3)2Cl2Ru=CHPh [10], first by Grubbs and co-workers the range of these catalysts was broadened because of their tolerancy towards heteroatom ligands and the possibility to work

• Table 2), is due to the coordination of the O atom of the substrate in 14–19. In other words, with a heteroatom containing substrate the heteroatom can coordinate to the Ru center, as in the Hoveyda-type precatalysts [6], maybe stabilizing the active species, see Figure 3a. In any case, coordination of

• overall uphill path. Coordination of the terminal C=C double bond with respect to coordination of the O heteroatom is disfavored by 4.5 kcal/mol in 14 and favored by 1.8 kcal/mol in 16, respectively. The transition states are 20.2 and 19.9 kcal/mol higher in energy with respect to the 14e species, and the

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

• -substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• (Figure 2). These columns are linked together along c-axis through hydrogen bonding occurring between TTF-C-H and NO2 (TTF-C–H1···O3-NO 2.493(6) Å). In the b-direction, the columns of stacked head to tail molecules are connected laterally through S···O heteroatom contacts (d = 3.16 Å, Figure S1

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• attachment of the alkyl chain to the aromatic system. In this review we are not discussing orthocyclophanes but rather focus on meta- and paracyclophanes only. The aromatic ring present in the cyclophane system can be either heterocyclic or carbocylic in nature. If there is a heteroatom present in the

• aromatic ring system then the system is called a heterophane (9) [54][55][56], whereas if the heteroatom is present in the alkyl chain of the bridge, then it is called a heteraphane (10) [57][58][59][60]. Alternatively, if the heteroatom is present in both the aromatic ring and the alkyl chain, it is

• new synthetic methods in this area is considered a useful exercise. To this end, name reactions or popular reactions, and rearrangement reactions are widely used. In connection with the synthesis of cyclophanes, we describe the employment of these reactions for C–C or C–heteroatom-bond formation. The

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• , led to the production of superconducting salts based on TTF type donors containing a heteroatom such as sulfur, selenium, oxygen, etc. [17][18][19][20]. Among a large number of tetrathiafulvalene analogues, bis(ethyleneditiho)tetrathiafulvalene (BEDT-TTF, 3), also known as ET, has been the most

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• involved in C–O coupling reactions of the same type, the classification according to the structures of O-reagents is inconvenient and was not applied. Some cross-dehydrogenative C–O coupling reactions are cursorily described in reviews on the oxidative C–heteroatom bond formation without the use of metal

Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

• Bin Yin,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12

• using ionic liquid poly(HF) salts such as Et3N·nHF and Et4NF·nHF (n = 3–5) as supporting electrolyte and fluorine source [9][10][11], and we have systematically studied the anodic fluorination of various heteroatom-containing compounds including heterocycles and macromolecules so far [12][13][14][15][16

• ][17][18][19][20]. More than 20 years ago, we reported the first successful example of the electrochemical selective fluorination of heteroatom-containing compounds such as α-(phenylthio)ester and its analogues as shown in Scheme 1 [21][22]. Furthermore, anodic fluorodesulfurization of dithioacetals

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

Beilstein J. Org. Chem. 2014, 10, 2858–2873, doi:10.3762/bjoc.10.303

• enormous strain and is therefore susceptible to ring-opening reactions with a variety of nucleophiles [3][4]. Such transformations lead to 1,2-heteroatom structures which are often found in pharmaceuticals and natural products. Yudin et al. described an electrochemical aziridination process where an

Binding mode and free energy prediction of fisetin/β-cyclodextrin inclusion complexes

• Bodee Nutho,
• Wasinee Khuntawee,
• Chompoonut Rungnim,
• Piamsook Pongsawasdi,
• Peter Wolschann,
• Alfred Karpfen,
• Nawee Kungwan and
• Thanyada Rungrotmongkol

Beilstein J. Org. Chem. 2014, 10, 2789–2799, doi:10.3762/bjoc.10.296

• value of 30–50°). Solvation In this study, the radial distribution function (RDF, gij(r)) calculation was used to monitor the water molecules (the oxygen atom of water j) in the spherical radius r of the fisetin heteroatom (oxygen atom i) in each complex. The RDF plots coupled with the integration

Gold(I)-catalysed synthesis of a furan analogue of thiamine pyrophosphate

• Amjid Iqbal,
• El-Habib Sahraoui and
• Finian J. Leeper

Beilstein J. Org. Chem. 2014, 10, 2580–2585, doi:10.3762/bjoc.10.270

• carbon–heteroatom bonds makes the method an appealing strategy towards diverse chemical targets [21][22][23][24][25][26][27][28][29][30]. Furthermore, the catalysts are stable to air and moisture and the reactions generally proceed under mild conditions. Aponick and co-workers reported a catalytic

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

• Roman Matthessen,
• Jan Fransaer,
• Koen Binnemans and
• Dirk E. De Vos

Beilstein J. Org. Chem. 2014, 10, 2484–2500, doi:10.3762/bjoc.10.260

• one [75]. In case the carbonyl or imine compound is reduced first, the negative charge may reside either on the carbon or on the heteroatom. This results in a first CO2 fixation on the carbon or on the heteroatom, depending on the electron-withdrawing/electron-donating properties of the substituents

Synthesis of novel conjugates of a saccharide, amino acids, nucleobase and the evaluation of their cell compatibility

• Dan Yuan,
• Xuewen Du,
• Junfeng Shi,
• Ning Zhou,
• Abdulgader Ahmed Baoum and
• Bing Xu

Beilstein J. Org. Chem. 2014, 10, 2406–2413, doi:10.3762/bjoc.10.250

• unique types of heteroatom aromatics, not only promote self-assembly [30], but also have the capability for DNA delivery [16]. To examine the role of the saccharide, we also designed and synthesized the respective conjugates of amino acids and nucleobase without the glucuronic moiety (5–8) for comparison

N–O Cleavage reactions of heterobicycloalkene-fused 2-isoxazolines

• Jaipal R. Nagireddy,
• Geoffrey K. Tranmer,
• Emily Carlson and
• William Tam

Beilstein J. Org. Chem. 2014, 10, 2200–2205, doi:10.3762/bjoc.10.227

• heteroatom of the bicycloalkene rather than to the nitrogen of the isoxazoline, reducing its tendency toward N–O cleavage. Furthermore, since the reaction did not proceed in the absence of either AlCl3 or nickel, coordination of both metals appears to be an essential step in the formation of 16. Under the

• optimized conditions, we suggest that initial binding of Lewis acidic aluminum to the bridge heteroatom of 10 leaves its isoxazoline nitrogen free to interact with the Raney nickel (Scheme 5, 23). The N–O bond is subsequently broken to afford 24, and it is conceivable at this stage that the added

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• of carbon–carbon and carbon–heteroatom bond-forming transformations [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these

• highly functionalized cyclopentenes that bear an array of heteroatom-substituted quaternary stereocenters [36]. From a screening of catalysts, they carefully examined the effect of substitution of the binaphthyl framework of chiral phosphines, identifying the 3,3´-diphenyl-substituted phosphepine B4 as

• 1,1-disubstituted olefins proceeded smoothly to give functionalized cyclopentenes in satisfactory yields with up to 98% ee (Scheme 3). That study extended the substrate scope of known asymmetric phosphine-catalyzed [3 + 2] annulation reactions to diverse heteroatom-substituted olefins and allenamides

Photorelease of phosphates: Mild methods for protecting phosphate derivatives

• Sanjeewa N. Senadheera,
• Abraham L. Yousef and
• Richard S. Givens

Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

• organic chemistry and biochemistry, but they are particularly important for mechanistic studies in biochemistry and biophysics [6][8][9][10][11]. Most PPG candidates require sufficiently high energy excited states for heterolysis of a carbon–oxygen or carbon–heteroatom bond that binds the chromophore to a