Learning from B₁₂ enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

• Keishiro Tahara,
• Ling Pan,
• Toshikazu Ono and
• Yoshio Hisaeda

Beilstein J. Org. Chem. 2018, 14, 2553–2567, doi:10.3762/bjoc.14.232

• carboxylic ester-migrated product was formed via not a radical, but a cationic intermediate that was generated by the fragmentation to the monoalkylated complex at the anode (Scheme 2). 2-2. Artificial enzyme-mediated reactions A vesicle-type B12 artificial enzyme was constructed by combining bilayer

Synthesis of aryl sulfides via radical–radical cross coupling of electron-rich arenes using visible light photoredox catalysis

• Amrita Das,
• Mitasree Maity,
• Simon Malcherek,
• Burkhard König and
• Julia Rehbein

Beilstein J. Org. Chem. 2018, 14, 2520–2528, doi:10.3762/bjoc.14.228

• , indicating that probably a fragmentation of the disulfide bond took place due to the laser irradiation. Since this effect occurred also under reduced laser power (70% of the original 58 mJ/pulse) we restricted the current analysis to the two-component solution (A). Since 1,3,5-TMB did not show any transient

Diazirine-functionalized mannosides for photoaffinity labeling: trouble with FimH

• Femke Beiroth,
• Tomas Koudelka,
• Thorsten Overath,
• Stefan D. Knight,
• Andreas Tholey and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2018, 14, 1890–1900, doi:10.3762/bjoc.14.163

• hydrolyzed carbene. However, MS/MS fragmentation of both the unmodified peptide (567.3281)2+ and the allegedly modified peptide (832.4043)2+ exhibited the same b- and y-ion series (cf. Supporting Information File 1, Figure S10). Accordingly, the low intensity peak is most likely the result of non-covalent

Efficient catenane synthesis by cucurbit[6]uril-mediated azide–alkyne cycloaddition

• Antony Wing Hung Ng,
• Chi-Chung Yee,
• Kai Wang and
• Ho Yu Au-Yeung

Beilstein J. Org. Chem. 2018, 14, 1846–1853, doi:10.3762/bjoc.14.158

• upfield shifted triazole 1H NMR resonances of Cat-2–Cat-10 at ca. 6.4 ppm are consistent with the inclusion of the triazole in the CB[6] cavity [22][24][25]. The ESIMS, HRMS and MS2 spectra are all consistent with the [3]catenanes with a similar fragmentation behavior as that of Cat-1. The 1H NMR, 13C NMR

The phenyl vinyl ether–methanol complex: a model system for quantum chemistry benchmarking

• Dominic Bernhard,
• Fabian Dietrich,
• Mariyam Fatima,
• Cristóbal Pérez,
• Hannes C. Gottschalk,
• Axel Wuttke,
• Ricardo A. Mata,
• Martin A. Suhm,
• Melanie Schnell and
• Markus Gerhards

Beilstein J. Org. Chem. 2018, 14, 1642–1654, doi:10.3762/bjoc.14.140

• broadened and affected by ionization-induced fragmentation of larger clusters (cf. Figure S1b, Supporting Information File 1). This is also reflected in the recorded IR/R2PI spectra (cf. Figure S2, Supporting Information File 1), yielding solely the spectrum shown in Figure 4 via the excitation energy of

• would coincide with the fragmentation-dominated region of the R2PI spectrum, where, however, only signatures of larger clusters could be identified. These considerations strengthen the arguments for the presence of an OH∙∙∙O structure laid before, on the basis of the computed coupled cluster energies

• elusiveness would be a low interconversion barrier. However, rotational spectroscopy further reveals the presence of the OH–P isomer as a second isomer, being less populated, which is not observed with the less sensitive FTIR technique and might be superimposed by fragmentation of larger clusters in the

Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• , similar deformylation by action of hypervalent iodine has also been demonstrated: the β-fragmentation reaction of an anomeric alkoxy radical of carbohydrates was mediated by a hypervalent iodine reagent [73]. The reaction results in the formation of carbohydrates with a reduction of one carbon. From the

• the β-fragmentation of the C1–C2 bond. As a result, a C2 radical is generated and is further oxidized to a carbocation that is reacted with nucleophilic agents to give the desired products. Boto et al. applied the reaction to the one-pot synthesis of acyclic nucleosides that belong to an important

• class of nucleosides with antiviral activity [74]. First, they tried to synthesize acyclic nucleosides in a stepwise manner. The substrates 128 and 129 for the fragmentation reaction were synthesized from ribose in a few steps by the conventional method. The oxidative scission of 128 and 129 was carried

Drug targeting to decrease cardiotoxicity – determination of the cytotoxic effect of GnRH-based conjugates containing doxorubicin, daunorubicin and methotrexate on human cardiomyocytes and endothelial cells

• Livia Polgár,
• Eszter Lajkó,
• Pál Soós,
• Orsolya Láng,
• Marilena Manea,
• Béla Merkely,
• Gábor Mező and
• László Kőhidai

Beilstein J. Org. Chem. 2018, 14, 1583–1594, doi:10.3762/bjoc.14.136

• fragmentation of the conjugate between the aglycon part and sugar moiety resulted in fragments in which the peptide was attached either the aglycon OH group or the amino group of sugar moiety [23]. When unprotected Dox was used for the reaction with glutaric anhydride, the amino group was modified with glutaric

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

• including the cleavage of the triple bond and the fragmentation of the carboxylate unit, would finally lead to the furans 24 and the formamide 25. The group of Waser has discovered an atom-economical multi-component process between alkynylbenziodoxolones 22 and diazo compounds, which is catalyzed by the

Investigations of alkynylbenziodoxole derivatives for radical alkynylations in photoredox catalysis

• Yue Pan,
• Kunfang Jia,
• Yali Chen and
• Yiyun Chen

Beilstein J. Org. Chem. 2018, 14, 1215–1221, doi:10.3762/bjoc.14.103

• (Scheme 4). Tertiary alcohols 6 were reported to be activated by cyclic iodine(III) reagents under photoredox conditions to generate alkoxyl radicals, and subsequently underwent β-fragmentation and alkynylation to yield 7 after eliminating the arylketone [25]. With tertiary alcohol 6a as the alkyl radical

• ’-alkyne 3a gave a slightly lower 63% yield of 9 [21]. β-Ketone alcohols 10 were reported to be activated by cyclic iodine(III) reagents under photoredox conditions to generate alkoxyl radicals, and subsequently underwent β-fragmentation and alkynylation to yield ynone 9 [26]. The unsubstituted BI-alkyne

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

• Elsa Deruer,
• Vincent Hamel,
• Samuel Blais and
• Sylvain Canesi

Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101

• , decarboxylation, and fragmentation [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. The sulfonate group is a useful functionality frequently employed as a leaving group in substitution reactions. Production of sulfonates [28] from alcohols generally involves reaction with a

On the design principles of peptide–drug conjugates for targeted drug delivery to the malignant tumor site

• Eirinaios I. Vrettos,
• Gábor Mező and
• Andreas G. Tzakos

Beilstein J. Org. Chem. 2018, 14, 930–954, doi:10.3762/bjoc.14.80

Anodic oxidation of bisamides from diaminoalkanes by constant current electrolysis

• Tatiana Golub and
• James Y. Becker

Beilstein J. Org. Chem. 2018, 14, 861–868, doi:10.3762/bjoc.14.72

• RCONHCH2OCH3. Moreover, upon replacing LiClO4 with Et4NBF4 an additional fragmentation type of product was generated from the latter amides, namely RCONHCHO. Also, the anodic process was found to be more efficient with C felt as the anode, and in a mixture of 1:1 methanol/acetonitrile co-solvents. Keywords

• spectrum of products obtained is described in Scheme 8. Except for the expected monomethoxylated II-3a and dimethoxylated II-3b products, fragmentation products (II-3c, 3d, 3e) were observed too. Table 2 below summarizes the type of products and their relative ratios obtained from initial electrochemical

• comparison to the above results, oxidation of II-3 on a Pt anode (Table 2, entries 3 and 4) affords similar products but with less selectivity because of the formation of an additional fragmentation product, benzoic acid (II-3e) in 10–20% yield. Other anodes were tested as well (Table 2, entries 5–7) at an

Cobalt-catalyzed directed C–H alkenylation of pivalophenone N–H imine with alkenyl phosphates

• Wengang Xu and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2018, 14, 709–715, doi:10.3762/bjoc.14.60

• alkenylation reaction, affording the product 3aj with an E/Z ratio of 4:1. In our previous study on the C–H alkylation and arylation of pivalophenone N–H imines, we demonstrated that the pivaloyl imine readily undergoes fragmentation into a cyano group via an iminyl radical under peroxide photolysis or copper

Electrochemical Corey–Winter reaction. Reduction of thiocarbonates in aqueous methanol media and application to the synthesis of a naturally occurring α-pyrone

• Ernesto Emmanuel López-López,
• José Alvano Pérez-Bautista,
• Fernando Sartillo-Piscil and
• Bernardo A. Frontana-Uribe

Beilstein J. Org. Chem. 2018, 14, 547–552, doi:10.3762/bjoc.14.41

• formed by β-fragmentation of radical anion F, is maximum when is locked in an antiperiplanar conformation (Scheme 4). Therefore, this electrochemical reaction represents a promising way to produce trans-olefins from their respective thiocarbonates, overcoming thus the toxicity and safety issues of the

Polarization spectroscopy methods in the determination of interactions of small molecules with nucleic acids – tutorial

• Tamara Šmidlehner,
• Ivo Piantanida and
• Gennaro Pescitelli

Beilstein J. Org. Chem. 2018, 14, 84–105, doi:10.3762/bjoc.14.5

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

• gave better yields than their bromo or chloroanalogues, because of their higher fragmentation stability after single-electron reduction. Disulfides Formation of sulfides Jacobi von Wangelin and co-workers published a photocatalyzed protocol for the formation of aryl sulfides from the respective aryl

Structural diversity in the host–guest complexes of the antifolate pemetrexed with native cyclodextrins: gas phase, solution and solid state studies

• Magdalena Ceborska,
• Magdalena Zimnicka,
• Aneta Aniela Kowalska,
• Kajetan Dąbrowa and
• Barbara Repeć

Beilstein J. Org. Chem. 2017, 13, 2252–2263, doi:10.3762/bjoc.13.222

• available in Supporting Information File 1, Figure S2a–c). The exclusive fragmentation pathway of studied complexes into two components suggests that PTX is quite loosely connected with the CD comparing to a typical rotaxane complex for which the main fragmentations, occurring at substantial high collision

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• 114 [224] or chitosan 115 [225]. The functionalization of polyacrylamide obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization was also recently reported to produce 116 (Figure 31). However, the conditions of the Moedritzer–Irani reaction induced the hydrolysis of the

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

• Sadaf Hanif,
• Bernd Oschmann,
• Dmitri Spetter,
• Muhammad Nawaz Tahir,
• Wolfgang Tremel and
• Rudolf Zentel

Beilstein J. Org. Chem. 2017, 13, 1693–1701, doi:10.3762/bjoc.13.163

• about controlled/living radical polymerization, like nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer polymerization (RAFT) [2]. In general, by controlled radical polymerization techniques it is possible to prepare

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• SET mechanism to generate a radical cation B, followed by fragmentation to afford 12 (Scheme 3b). Either of these processes provided the imine moiety, along with o-iodosobenzoic acid (IBA, Scheme 3). In general, IBX-mediated oxidative dehydrogenation is conducted at high temperatures (>50 °C

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

• family known to date. A structure was proposed by the Small group based on mass fragmentation and 1H/2D NMR spectroscopic data. This structure, which features a tetraenoate (lower) side chain with a terminal 1,3-diol motif was once again confirmed by total synthesis in the Kishi laboratory; the relative

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• water addition). Possible fragmentation of the [Rh] catalyst is indicated. FhuA ΔCVFtev was analyzed after digestion by protease from Tobacco Etch Virus (TEV). Coupling of [Rh]-1 to the open channel protein FhuA ΔCVFtev. SDS, sodium dodecyl sulfate; THF, tetrahydrofuran. Comparison of common

Grip on complexity in chemical reaction networks

• Albert S. Y. Wong and
• Wilhelm T. S. Huck

Beilstein J. Org. Chem. 2017, 13, 1486–1497, doi:10.3762/bjoc.13.147

• ), trypsin-catalyzed conversion of a rhodamine substrate (S) to a fluorescent product (P) in the presence of a strong inhibitor (soybean trypsin inhibitor, STI), and trypsin-catalyzed fragmentation of a polycation (in purple) in the presence of a polyanion (in cyan). Adapted with permission from [94

A new member of the fusaricidin family – structure elucidation and synthesis of fusaricidin E

• Marcel Reimann,
• Louis P. Sandjo,
• Luis Antelo,
• Eckhard Thines,
• Isabella Siepe and
• Till Opatz

Beilstein J. Org. Chem. 2017, 13, 1430–1438, doi:10.3762/bjoc.13.140

• removed to yield the natural product 1. HPLC analysis showed only a single peak with the same retention time, mass and fragmentation pattern as the natural product. After purification by preparative HPLC, NMR spectroscopy confirmed that the assumed structure and stereochemistry of the natural product was

• of the respective products. Structure of fusaricidins E (1) and F (2). NOESY /COSY and HMBC correlations of compound 1. Fragmentation pattern of compounds 1 and 2. Byproducts from removal of Cbz group in THF and DMF. Retrosynthetic plan for the depsipeptide and GHPD side chain. a) LiAlH4, THF, reflux

Construction of highly enantioenriched spirocyclopentaneoxindoles containing four consecutive stereocenters via thiourea-catalyzed asymmetric Michael–Henry cascade reactions

• Yonglei Du,
• Jian Li,
• Kerong Chen,
• Chenglin Wu,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2017, 13, 1342–1349, doi:10.3762/bjoc.13.131

• -catalyzed Michael addition/intramolecular silyl nitronate-olefin cycloaddition (ISOC)/fragmentation sequence to produce highly enantioenriched spirocyclopentaneoxindoles containing an oxime functional group from easily accessible 3-allyl-substituted oxindoles and nitroolefins, which has received wide