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

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• -coupling; cyanoarenes; reactive intermediates; reductive alkylation; Introduction Alkylcyanobiphenyls are well known largely due to their mesogenic properties, which were discovered by Gray in the 1970th [1][2]. Alkylcyanobiphenyls and their analogs (e.g., dialkyl and alkoxy alkyl derivatives) are still

The EIMS fragmentation mechanisms of the sesquiterpenes corvol ethers A and B, epi-cubebol and isodauc-8-en-11-ol

• Patrick Rabe and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2016, 12, 1380–1394, doi:10.3762/bjoc.12.132

• to 3c+·, followed by α-cleavage to F3+·. Two subsequent hydrogen rearrangements result in the conjugated reactive intermediates G3+· and H3+·, which may be followed by the elimination of water to I3+· that upon α-cleavage yields the benzyl cation J3+. Finally, PMA43 reveals a clean formation of the

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

• Sean P. Bew,
• Glyn D. Hiatt-Gipson,
• Graham P. Mills and
• Claire E. Reeves

Beilstein J. Org. Chem. 2016, 12, 1081–1095, doi:10.3762/bjoc.12.103

• rac-3 (Scheme 1). The formation and reaction of these reactive intermediates with NO generates O3 and mixtures of IPNs, i.e., rac-7–(E)-10 (Scheme 1). Contributing to the complexity of the climate chemistry associated with 1 is its oxidation to ketones, e.g., 11 and rac-6 and aldehydes, e.g., rac-5

(Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers

• Giorgos Koutoulogenis,
• Nikolaos Kaplaneris and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2016, 12, 462–495, doi:10.3762/bjoc.12.48

• of intermediates have been proposed to be the reactive intermediates in many reactions such as aldol, Michael, Mannich, and α-functionalization (α-chlorination, α-amination, α-fluorination) reactions. Proline-type organocatalysts are considered priviliged, because their corresponding enamines exist

Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions

• Rajeev S. Menon,
• Akkattu T. Biju and
• Vijay Nair

Beilstein J. Org. Chem. 2016, 12, 444–461, doi:10.3762/bjoc.12.47

• ]. Meanwhile, the Breslow intermediate is produced from the aldehyde by the thiazolium 31-derived NHC. The union of these two reactive intermediates furnished α-amidoketones 32 in excellent yields (Scheme 18). A diastereoselective [4 + 1] annulation of phthalaldehyde with imines leading to the formation of cis

Dynamic behavior of rearranging carbocations – implications for terpene biosynthesis

• Stephanie R. Hare and
• Dean J. Tantillo

Beilstein J. Org. Chem. 2016, 12, 377–390, doi:10.3762/bjoc.12.41

• have pointed to the possibility that inherent dynamical tendencies of reactive intermediates may play important roles in enzyme evolution. Here we review key studies on the dynamical behavior of carbocations. First we provide an introduction to dynamical behavior and how it is examined using modern

• reactive intermediates often meet this criterion and exhibit what are called “non-statistical dynamic effects”, that is, product distributions that cannot be rationalized by traditional TST [19][29][30]. These effects (highlighted through the examples discussed below) are typically described using

Copper-mediated synthesis of N-alkenyl-α,β-unsaturated nitrones and their conversion to tri- and tetrasubstituted pyridines

• Dimitra Kontokosta,
• Daniel S. Mueller,
• Dong-Liang Mo,
• Wiktoria H. Pace,
• Rachel A. Simpson and
• Laura L. Anderson

Beilstein J. Org. Chem. 2015, 11, 2097–2104, doi:10.3762/bjoc.11.226

• hydroxylamines, as well as N-alkenyl and N-arylnitrones [1][2][3][4][5]. We have discovered that when this transformation is performed with oxime and hydroxamic acid substrates, these reactive intermediates can be accessed and subsequently rearrange to a variety of challenging organic fragments and heterocyclic

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

• Roberto Blanco Trillo,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2015, 11, 313–322, doi:10.3762/bjoc.11.36

• , in Pd catalysts. Keywords: chirality; hydrolysis; phosphorus; rearrangements; terpenoids; Introduction Phosphorus halides are highly reactive intermediates for the synthesis of phosphites and phosphoramidites [1][2][3][4][5], which are widely used, for example, as ligands in catalysts [6][7][8][9

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

• of the generated reactive intermediates and assist in the formation of the desired products. Tin, silicon or sulfur-based electroauxiliaries have proved useful in this endeavour. Yoshida and co-workers developed an organothio electroauxiliary that is selectively cleaved under anodic oxidation

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

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

• substrate is electrochemically inactive. In many cases, undesired side-reactions can be avoided by using redox mediators, since reactive intermediates do not accumulate on the electrode surface. Moreover, the indirect approach is often used in order to inhibit electrode passivation caused by formation of

• nucleophilic trapping of anodically formed iminium (23) or alkoxycarbenium species (24). The reactive intermediates can be generated directly from ethers or carboxylic acid amides (Scheme 9) [32]. However, aliphatic ethers and amides generally exhibit high oxidation potentials, and a large number of functional

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

• hazardous reducing agents by clean electrons. In this case, the high thermodynamic stability of CO2 is by-passed by a simple one-electron reduction at an electrode, leading to in situ generation of reactive intermediates. Often, room temperature conditions are sufficient, considering that the energy of the

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• reactive intermediates or assist the reduction–elimination step [80][82]. Conclusion In conclusion, we have shown that the cavity-shaped phosphines HUGPHOS-1 and HUGPHOS-2 exclusively form monophosphine complexes with Pd(II), Pt(II), Rh(I), and Ru(II) cations. In all these complexes, the CD cavity tightly

Photochemical approach to functionalized benzobicyclo[3.2.1]octene structures via fused oxazoline derivatives from 4- and 5-(o-vinylstyryl)oxazoles

• Ivana Šagud,
• Simona Božić,
• Željko Marinić and
• Marija Šindler-Kulyk

Beilstein J. Org. Chem. 2014, 10, 2222–2229, doi:10.3762/bjoc.10.230

• framework of numerous important biologically active natural compounds or their metabolites [1]. Properly functionalized bicyclo[3.2.1]octanes have proved as useful reactive intermediates in stereoselective transformations making these derivatives powerful building blocks in organic synthetic strategies [2

A new charge-tagged proline-based organocatalyst for mechanistic studies using electrospray mass spectrometry

• J. Alexander Willms,
• Rita Beel,
• Martin L. Schmidt,
• Christian Mundt and
• Marianne Engeser

Beilstein J. Org. Chem. 2014, 10, 2027–2037, doi:10.3762/bjoc.10.211

• quite a number of different species. Side products, off-cycle resting states, reagent degradation products and impurities of various origins may be present in much higher concentration than the interesting reactive intermediates. Thus, ESI spectra of reacting solutions can be frustratingly complicated

Isoxazolium N-ylides and 1-oxa-5-azahexa-1,3,5-trienes on the way from isoxazoles to 2H-1,3-oxazines

• Alexander F. Khlebnikov,
• Mikhail S. Novikov,
• Yelizaveta G. Gorbunova,
• Ekaterina E. Galenko,
• Kirill I. Mikhailov,
• Viktoriia V. Pakalnis and
• Margarita S. Avdontceva

Beilstein J. Org. Chem. 2014, 10, 1896–1905, doi:10.3762/bjoc.10.197

• isoxazolium N-ylides from N-unsubstituted isoxazole derivatives. The formation of such ylides as reactive intermediates in the reactions of bases on isoxazolium salts was earlier supposed [6][7][8][9]. However, the detection of isoxazolium N-ylides has never been reported. Recently, we found an alternative

Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu₃C₆H₂P=C: and effects of conjugation between the P=C and aromatic moieties

• Masaaki Yoshifuji and
• Shigekazu Ito

Beilstein J. Org. Chem. 2014, 10, 1032–1036, doi:10.3762/bjoc.10.103

• cyclization of 1 would be necessary to develop the chemistry of reactive intermediates containing low-coordinated heavier main group elements [17]. Additionally, the structure of 2 is expected to be quite unique as the P=C π-system is nearly coplanar with the aromatic ring. In our previous paper, unique photo

Thermodynamically stable [4 + 2] cycloadducts of lanthanum-encapsulated endohedral metallofullerenes

• Yuta Takano,
• Yuki Nagashima,
• M. Ángeles Herranz,
• Nazario Martín and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2014, 10, 714–721, doi:10.3762/bjoc.10.65

• Discussion Synthesis and characterization of La2@C80 cycloadducts o-Quinodimethanes 2a and 2b were generated in situ by thermolysis of the corresponding sultines 1a and 1b in toluene at 80 °C (Scheme 1). The highly reactive intermediates are trapped efficiently by La2@C80, which acts as a dienophile to form

Flow microreactor synthesis in organo-fluorine chemistry

• Hideki Amii,
• Aiichiro Nagaki and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2013, 9, 2793–2802, doi:10.3762/bjoc.9.314

• characteristic features of microstructures are responsible for their effectiveness. In particular, brilliant works of the generation and reactions of reactive intermediates that cannot be done in batch reactors have been developed by means of ‘space integration methodology’, where a sequence of reactions is

• which allow the generation and reactions of reactive intermediates before decomposition. By virtue of these characteristic features, the residence time control in flow microreactors makes the generation of highly reactive species possible, including their reactions on a preparative scale within a second

The chemistry of amine radical cations produced by visible light photoredox catalysis

• Jie Hu,
• Jiang Wang,
• Theresa H. Nguyen and
• Nan Zheng

Beilstein J. Org. Chem. 2013, 9, 1977–2001, doi:10.3762/bjoc.9.234

• Jie Hu Jiang Wang Theresa H. Nguyen Nan Zheng Department of Chemistry, University of Arkansas, Fayetteville, AR 72701, USA 10.3762/bjoc.9.234 Abstract Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some

• initialize radical polymerization of HEA. Because of ring strain, cyclopropanes are prone to ring opening via cleavage of one of the three C–C bonds. The resulting reactive intermediates have been shown to participate in a number of synthetic/mechanistic applications [103][104]. One of these applications is

• electron strictly dependent upon the small molecules encountered. Amines typically act as an electron donor to reductively quench the photoexcited state while they are oxidized to the corresponding amine radical cations. The resulting nitrogen radical cations are highly useful reactive intermediates that

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

• Kegong Ji,
• Jonathan Nelson and
• Liming Zhang

Beilstein J. Org. Chem. 2013, 9, 1925–1930, doi:10.3762/bjoc.9.227

• carboxylate; Introduction We reported in 2010 [1] that α-oxo gold carbenes could be conveniently generated as reactive intermediates in gold-catalyzed intermolecular oxidation of alkynes. By using pyridine N-oxides [1] and later 8-substituted quinoline N-oxides [2] as the external oxidants, this approach

Damage of polyesters by the atmospheric free radical oxidant NO₃^•: a product study involving model systems

• Catrin Goeschen and
• Uta Wille

Beilstein J. Org. Chem. 2013, 9, 1907–1916, doi:10.3762/bjoc.9.225

• environmental conditions, however, NO3• is not an isolated reactant, but is always accompanied by other radicals and non-radical oxidants, such as NO2•, O3, and O2, respectively, which principally could become involved in these reactions through trapping of reactive intermediates. Thus, in order to explore the

• pathway yields the nitromethylene compound 15, which is formed via benzyl radical 7. Although we have not studied the nature of the reactive intermediates formed in these reactions, it is difficult to rationalize formation of the ring-substituted products 12–14 through a mechanism that involves benzylic

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

• Helga Seyler,
• Jegadesan Subbiah,
• David J. Jones,
• Andrew B. Holmes and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170

• mixing of reagents, boosting reaction rates, and safe handling of reactive intermediates. Using a commercial continuous-flow tube reactor [19], we have already demonstrated multigram synthesis of fullerene derivatives by cycloaddition reactions [11] as well as rapid conjugated-polymer synthesis using

Isolation and X-ray characterization of palladium–N complexes in the guanylation of aromatic amines. Mechanistic implications

• Abdessamad Grirrane,
• Hermenegildo Garcia and
• Eleuterio Álvarez

Beilstein J. Org. Chem. 2013, 9, 1455–1462, doi:10.3762/bjoc.9.165

• catalysis; palladium complexes; reactive intermediates; Introduction N-Arylguanidines are important compounds with interesting biological activities [1][2] such as fungicides [3] and also in supramolecular chemistry as complementary partners of carboxylate and nitro groups [4][5][6][7]. Some of these

True and masked three-coordinate T-shaped platinum(II) intermediates

• Manuel A. Ortuño,
• Salvador Conejero and
• Agustí Lledós

Beilstein J. Org. Chem. 2013, 9, 1352–1382, doi:10.3762/bjoc.9.153

• . Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C–H bond-activation processes. Keywords: C–H bond activation; intermediate; platinum(II); reactive intermediates; three-coordinate; T-shaped; Review