Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• the conversion of allenes 20. A regioselective 1,2-addition on the internal π-bond was observed to afford the products 21, because of the presence of a heteroatom substituent that can stabilize the radical or cationic intermediate by coordination with the copper complex (Scheme 9) [42]. However, the

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst

• Kimihiro Komeyama,
• Shunsuke Sakiyama,
• Kento Iwashita,
• Itaru Osaka and
• Ken Takaki

Beilstein J. Org. Chem. 2018, 14, 1413–1420, doi:10.3762/bjoc.14.118

• -selectivity because of meta- and ortho-substituted aryl iodides also being well tolerated in the reaction. The protocol was not only limited to the coupling of simple allenes; it was also used with heteroatom-containing functionalized allenes to afford the syn-homoallylic alcohols 4u, 4u’ and 4w in reasonably

Atom-economical group-transfer reactions with hypervalent iodine compounds

• Andreas Boelke,
• Peter Finkbeiner and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108

• monoarylations, produces not only the aryl iodide, but also stoichiometric amounts of salt side-products, limiting the AE of these transformations to roughly 10–20% (Scheme 1, reaction (a)). In the second case, both organic residues (one carbon or heteroatom ligand plus the arene of the former aryl-λ3-iodane or

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: synthesis of vicinal-dichlorides and chlorodienes

• Zhensheng Zhao and
• Graham K. Murphy

Beilstein J. Org. Chem. 2018, 14, 796–802, doi:10.3762/bjoc.14.67

• - and vinyl chlorides are highly sought-after intermediates for effecting allylations, and for use in transition metal-catalyzed carbon–carbon and carbon–heteroatom bond-forming reactions [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. Given the versatility of allyl chloride and β

Functionalization of N-arylglycine esters: electrocatalytic access to C–C bonds mediated by n-Bu₄NI

• Mi-Hai Luo,
• Yang-Ye Jiang,
• Kun Xu,
• Yong-Guo Liu,
• Bao-Guo Sun and
• Cheng-Chu Zeng

Beilstein J. Org. Chem. 2018, 14, 499–505, doi:10.3762/bjoc.14.35

• to a heteroatom (N or O) [6][7][8][9][10]. However, the oxidative C–C formation of secondary amines, especially amino acids has been more important for studying properties and functions of natural and non-natural amino acids [11]. Consequently, efficient and selective construction of C–C bonds of

The selective electrochemical fluorination of S-alkyl benzothioate and its derivatives

• Shunsuke Kuribayashi,
• Tomoyuki Kurioka,
• Shinsuke Inagi,
• Ho-Jung Lu,
• Biing-Jiun Uang and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2018, 14, 389–396, doi:10.3762/bjoc.14.27

• , Rozhkov and Laurent reported an electrochemical partial fluorination of naphthalene and olefins about 30 years ago [5][6]. However, at that time, there has been no report on the anodic fluorination of heteroatom-containing compounds. At almost the same time, we found that the anodic α-methoxylation of

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• conditions. The key concepts of photocatalysis and photoredox-catalyzed reactions for carbon–carbon and carbon–heteroatom (C–X) bond formation have been reviewed in detail. However, several new photocatalytic methods for the formation of carbon–sulfur (C–S) bonds were recently reported and we aim to

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• metal catalysts and/or a large excess of organic oxidants can be obstacles to production. In a quest for ideal conditions, Lei and co-workers exposed heteroatom-functionalised alkenes 14 to aerobic Cvinyl–heteroatom bond oxygenation under metal-free conditions, where oxygen from air worked in concert

• with a catalytic amount of potassium persulfate to activate CF3SO2Na (Scheme 7) [26]. The heteroatom must be a good leaving group or part of it (X = Br, Cl, NHCOMe, N3, OP(O)(OEt)2). A mechanistic investigation demonstrated the role of oxygen: 93% isotopic purity of the ketone product was obtained when

Recent progress in the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres

• Myriam Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2017, 13, 2637–2658, doi:10.3762/bjoc.13.262

• -workers proposed a variant of the defluorinative reaction using heteroatom nucleophiles using aluminum-based reagents such as Me2AlCl and (iPrO)2AlN3, and (Z) selectivity was observed for the formation of the monofluoroalkene [27]. When dimethylaluminum chloride was used, the resulting allylic chloride

Regiodivergent condensation of 5-alkoxycarbonyl-1H-pyrrol-2,3-diones with cyclic ketazinones en route to spirocyclic scaffolds

• Alexey Yu. Dubovtsev,
• Maksim V. Dmitriev,
• Аndrey N. Maslivets and
• Michael Rubin

Beilstein J. Org. Chem. 2017, 13, 2179–2185, doi:10.3762/bjoc.13.218

• (vinylogous carbonates and carbamates) normally requires more forcing conditions, but usually can be facilitated by addition of catalytic amounts of organic base (Scheme 2) [43]. Interestingly, we figured out that the presence of heteroatom X in the structure of enol 6 is important for the normal course of

Mechanochemical Knoevenagel condensation investigated in situ

• Sebastian Haferkamp,
• Franziska Fischer,
• Werner Kraus and
• Franziska Emmerling

Beilstein J. Org. Chem. 2017, 13, 2010–2014, doi:10.3762/bjoc.13.197

• reactions with quantitative yields of the final product are possible, rendering the use of solvents and work-up procedures unnecessary [3][15]. The mechanochemical synthesis can effect carbon–carbon and carbon–heteroatom covalent bonds, coordinating bonds between metal and ligands, and non-covalent

New bio-nanocomposites based on iron oxides and polysaccharides applied to oxidation and alkylation reactions

• Daily Rodríguez-Padrón,
• Alina M. Balu,
• Antonio A. Romero and
• Rafael Luque

Beilstein J. Org. Chem. 2017, 13, 1982–1993, doi:10.3762/bjoc.13.194

• applications in heterogeneous catalysis [10][11][12][13][14]. Transition metal and metal oxide nanoparticles have been reported to be highly active and selective in several processes, such as redox [15][16][17], C–C and C–heteroatom couplings [18][19]. In particular, iron oxide nanoparticles have been the

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• ], carbon–heteroatom [41][42], metal–ligand coordination bonds [43], non-covalent interactions such as hydrogen bonds or π–π arene stacking interactions [44], etc. are popularly known in literature. In this review the efforts are given towards documentation of various mechanochemical reactions like organic

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• palladium-catalysed heterogeneous hydrogenation [61]. In continuation of their elegant work on generating electrophilic heteroatom-transfer reagents in situ upon adding a heteroatom nucleophile to trichloroacetonitrile (compare with Scheme 11), Ooi’s group has recently also expanded this powerful concept to

An effective Pd nanocatalyst in aqueous media: stilbene synthesis by Mizoroki–Heck coupling reaction under microwave irradiation

• Carolina S. García,
• Paula M. Uberman and
• Sandra E. Martín

Beilstein J. Org. Chem. 2017, 13, 1717–1727, doi:10.3762/bjoc.13.166

• . Among them, cross-coupling and coupling reactions have been broadly applied for C–C and C–heteroatom bond formation [1][2][3][4][5][6]. These reactions have been proven to be powerful and attractive synthetic methods due to their high selectivity and tolerance to a wide range of functional groups on

• ). Despite that the synthesis of substituted heteroaryl derivatives is of great importance, only few examples employing heteroaryl halides in the Mizoroki–Heck reaction were reported [53]. This might be attributed to electronic aspects or poison by the heteroatom to the active Pd species [54]. However, when

Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 675–693, doi:10.3762/bjoc.13.67

• significantly, when compared to other reported heteroatom-doping syntheses, the fluorescence of the B-CDs was dynamically quenched by Fe3+ ions. Mechanistic studies suggested that a dynamic quenching model was prevalent at low concentrations due to interactions between Fe3+ and the CD surface, possibly

• simultaneously. For example, in 2015 Zhang et al. demonstrated that the energy intensive, hydrothermal treatment of glucose in the presence of glutathione (acting as both SPA and N/S heteroatom dopant) conducted at 180 °C for 22 h, resulted in CDs with QYs of up to 7%. The obtained CDs had blue-emissive

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• other hand, the C–H hydroxylation, either with heteroatom-containing directing groups or without directing groups, has provided various methods for the synthesis of phenols. Compared with traditional methods, the transition-metal-catalyzed phenol synthesis has several advantages: broad substrate scope

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

• -indanones and their heteroatom analogues 138–142 which may be further converted into biologically active compounds (Figure 4) [72]. Products 138–142 were obtained by electrocyclization of the substrates substituted by electron-withdrawing groups, such as CO2Me, P(O)(OEt)2, CN or NO2. This reaction was

Dimerization reactions of aryl selenophen-2-yl-substituted thiocarbonyl S-methanides as diradical processes: a computational study

• Michael L. McKee,
• Grzegorz Mlostoń,
• Katarzyna Urbaniak and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 410–416, doi:10.3762/bjoc.13.44

•  5). In conformer 12G, the diradical intermediate leading to product 13, where the two spins do couple, the spin density is 0.65 e−. As a model system to determine the effect of the heteroatom on the magnitude of the unpaired spin density, calculations were made for PhC(H)C4XH3, X = Se, S, O (16

• isolated from the reaction mixture. Thus, the presence of the heteroatom is of crucial importance for this new type of dimerization of aryl/hetaryl thiocarbonyl S-methanides of type 1 and this fact reflects the importance of so called ‘heavy atom effect’ [15] in the studied system. Stepwise, diradical

• interconvert readily. Potential competitive cyclization reactions of the intermediate diradical 12. a) Spin densities in the conformers 12F and 12G of diradical 12. b) Heteroatom effect on the magnitude of the spin density in the model diradical 16. Generation and typical reactions of the reactive dialkyl and

Chemical probes for competitive profiling of the quorum sensing signal synthase PqsD of Pseudomonas aeruginosa

• Michaela Prothiwa,
• Dávid Szamosvári,
• Sandra Glasmacher and
• Thomas Böttcher

Beilstein J. Org. Chem. 2016, 12, 2784–2792, doi:10.3762/bjoc.12.277

• of covalently reacting with the active site. We demonstrated the potential of our probes in a competitive labelling platform where we screened a library of synthetic HHQ and PQS analogues with heteroatom replacements and found several inhibitors of probe binding that may represent promising scaffolds

• synthetic HHQ and PQS derivatives with systematic heteroatom replacements [33]. Because the interactions of PqsD with AQs is still not entirely understood, we reasoned that HHQ or PQS analogues may be promising scaffolds for inhibitor development and we thus aimed to screen this library competitively

• the described procedures by McGlacken et al. [34] and Hradil et al. [35], respectively. We previously described the synthesis of HHQ and PQS derivatives with nitrogen in position 1 exchanged by oxygen and sulfur [33]. In our efforts to optimize the synthesis of these heteroatom derivatives we used a

A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

• Xiao Huang,
• Li Yang,
• Rikard Emanuelsson,
• Jonas Bergquist,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 2682–2688, doi:10.3762/bjoc.12.265

• conditions leading to exomethylene-EDOT [19]. Therefore, the usage of basic nucleophiles is problematic. Moreover, these heteroatom-based linkers between the polymer backbone and the pendant group usually have limited tolerance to acidic or basic conditions promoting hydrolysis, and some of them are

Et₃B-mediated and palladium-catalyzed direct allylation of β-dicarbonyl compounds with Morita–Baylis–Hillman alcohols

• Ahlem Abidi,
• Yosra Oueslati and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2402–2409, doi:10.3762/bjoc.12.234

• ; Morita–Baylis–Hillman; palladium; triethylborane; Introduction In nucleophilic allylic substitutions, π-allylpalladium complexes are useful intermediates for the construction of carbon–carbon and carbon–heteroatom bonds in organic synthesis [1]. Usually, palladium species are used as catalysts in the

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

• Lucie Brulíková,
• Aidan Harrison,
• Marvin J. Miller and
• Jan Hlaváč

Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184

• biologically active compounds. It is a variant of the Diels–Alder reaction where either the diene or the dienophile contains a heteroatom. Hetero-Diels–Alder reactions between conjugated dienes and nitroso dienophiles affording 1,2-oxazines are utilized for the synthesis of many biologically active molecules

• reactions of acylnitroso compounds in [4 + 2] cycloadditions indicate several facts. The copper–oxazoline complex behaves as an excellent catalyst for the aerobic oxidation of acylhydroxamic acids. However, this system is useful only for hydroxamic acids containing a heteroatom between the aryl and carbonyl

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

• unsubstituted at the 2-position (R2 = H) led to lower enanantioselectivity (84:16 to 87:13 er). Products were not observed when either α-heteroatom-substituted acroleins or 3-substituted indoles were used as starting materials. When either the enantioenriched or racemic products 138 were resubmitted to the

• additions to other classes of Michael acceptors only being reported more recently. While many examples using sulfur and carbon nucleophiles have been reported, the addition of other heteroatom nucleophiles remains relatively unexplored. This approach for the synthesis of tertiary carbon stereocenters