Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• copper(II) trifluoromethanesulfonate. The notable advantage of this protocol was that simple tosylamide had been directly used as amide nucleophile. The key point enabling the sulfonamidation transformation was the in situ generation of PhI=NTs (21) by employing PhI(OAc)2 in the reaction (Scheme 5

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• sulfur-containing molecules and since the early 1990s, tetrathiafulvalene (TTF) supramolecular chemistry. Before I went to Odense, the group had developed a very useful method of in situ generation of TTF thiolate anion from cyanoethylated precursors, which greatly simplifies the modification of the TTF

Copper-catalyzed aerobic radical C–C bond cleavage of N–H ketimines

• Ya Lin Tnay,
• Gim Yean Ang and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2015, 11, 1933–1943, doi:10.3762/bjoc.11.209

• of Grignard reagents to carbonitriles followed by protonation as one of the methods for in situ generation of N–H ketimines, which were directly subjected to Cu-catalyzed aerobic reactions without further purification [54]. In this way, biaryl N–H ketimines generated from biaryl-2-carbonitriles were

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH₄SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

• A. Srinivas Reddy and
• Kenneth K. Laali

Beilstein J. Org. Chem. 2015, 11, 1641–1648, doi:10.3762/bjoc.11.180

• catalyst for oxidative functionalization is comparatively less explored [11]. Notable examples of oxidative functionalization by Selectfluor include in situ generation of electrophile equivalents Cl+, Br+, SCN+ and NO2+ and their reactions with aromatics [12], the bromination of representative alkenes with

One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea

• Mohammad Abbasi and
• Reza Khalifeh

Beilstein J. Org. Chem. 2015, 11, 1265–1273, doi:10.3762/bjoc.11.141

• . On the other hand, the usual methods for preparing thioacids involve the action of toxic and unpleasant smelling, gaseous hydrogen sulfide on carboxylic acid derivatives [46][47]. Also, thioacids as thiols have a strong and repulsive smell. The in situ generation of thioacids using odourless, easy to

• thiourea and carboxylic acid derivatives to prepare thioacids has not yet been introduced. Hence, this work is focused on the development of new reaction sequences for the synthesis of thioacid derivatives via in situ generation of thioacids using thiourea as an inexpensive and easy to handle sulfur

• the thioester product cannot be produced through generation of the thioacid from thiourea and benzoyl chloride. To establish a protocol for the one-pot synthesis of thioacid derivatives via in situ generation of thioacids, considerable preliminary tests were accomplished using thiourea and carboxylic

The synthesis of active pharmaceutical ingredients (APIs) using continuous flow chemistry

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134

• transfer process even allowed this step to be performed on kilogram quantities of both starting materials (68, 69) at a reactor temperature of 35 °C giving the desired product 72 within a residence time of only 90 seconds. Vital to the successful outcome was the efficient in situ generation of LDA from n

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• reaction proceeds in analogy to the one for benzenic starting materials by in situ generation of the diene and reaction with surface π-bonds on the nanodiamond acting as dienophiles. The successful grafting can be monitored by the appearance of the distinct signal of nitriles in the IR spectrum at ~2225 cm

A general metal-free approach for the stereoselective synthesis of C-glycals from unactivated alkynes

• Shekaraiah Devari,
• Manjeet Kumar,
• Ramesh Deshidi,
• Masood Rizvi and
• Bhahwal Ali Shah

Beilstein J. Org. Chem. 2014, 10, 2649–2653, doi:10.3762/bjoc.10.277

• knowledge, this is the first report which descibres the in situ generation of trimethylsilylacetylene and its subsequent usage for C-alkynylation without the co-addition of a Lewis acid. The protocol may find application in a large number of reactions catalyzed by Lewis acid wherein pre-formed silylated

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

Expedient synthesis of 1,6-anhydro-α-D-galactofuranose, a useful intermediate for glycobiological tools

• Luciana Baldoni and
• Carla Marino

Beilstein J. Org. Chem. 2014, 10, 1651–1656, doi:10.3762/bjoc.10.172

• glycosylation via the in situ generation of galactofuranosyl iodide 10 (Scheme 2) [32][33][34][35]. Galactofuranosyl iodides were not previously described, and 10 proved to be useful for the synthesis of several D-Galf-containing molecules (Scheme 2) [32]. The reported procedure consisted in the treatment of

Microwave-assisted Cu(I)-catalyzed, three-component synthesis of 2-(4-((1-phenyl-1H-1,2,3-triazol-4-yl)methoxy)phenyl)-1H-benzo[d]imidazoles

• Yogesh Kumar,
• Vijay Bahadur,
• Anil K. Singh,
• Virinder S. Parmar,
• Erik V. Van der Eycken and
• Brajendra K. Singh

Beilstein J. Org. Chem. 2014, 10, 1413–1420, doi:10.3762/bjoc.10.145

• have a clear mechanistic proof. However, we believe that if the reaction proceed via route A in situ generation of Cu(I) [32][33] from Cu(II) takes place first upon reduction with D-glucose. Then, this Cu(I) reacts with 4-(prop-2-yn-1-yloxy)benzaldehyde 2a to form the copper acetylide [35][36] 5, which

Integration of enabling methods for the automated flow preparation of piperazine-2-carboxamide

• Richard J. Ingham,
• Claudio Battilocchio,
• Joel M. Hawkins and
• Steven V. Ley

Beilstein J. Org. Chem. 2014, 10, 641–652, doi:10.3762/bjoc.10.56

• such as 4 are fully reduced. For maximum efficiency further hydrogenation procedures were carried out at the lower flow rate 0.1 mL min−1 and higher temperature 100 °C. In situ generation of the intermediate Performing an optimisation experiment in continuous flow – such as described in the previous

Visible-light photoredox catalysis enabled bromination of phenols and alkenes

• Yating Zhao,
• Zhe Li,
• Chao Yang,
• Run Lin and
• Wujiong Xia

Beilstein J. Org. Chem. 2014, 10, 622–627, doi:10.3762/bjoc.10.53

• situ generation of bromine. Synthesis of dibromophenol product 2b''. Scope of the photocatalytic bromination of alkenes. Bromination of diketones and cyclization reactions. Survey of the photocatalytic bromination reaction conditions. Scope of the photocatalytic bromination of phenols. Supporting

• irradiated with blue LEDs (1 W) at room temperature open to air until the starting material disappeared completely (monitored by TLC). After the reaction was completed the solvent was concentrated in vacuo. The residue was purified by flash column chromatography to give the final product 8. Strategy for in

Isocyanide-based multicomponent reactions towards cyclic constrained peptidomimetics

• Gijs Koopmanschap,
• Eelco Ruijter and
• Romano V.A. Orru

Beilstein J. Org. Chem. 2014, 10, 544–598, doi:10.3762/bjoc.10.50

Silver and gold-catalyzed multicomponent reactions

• Giorgio Abbiati and
• Elisabetta Rossi

Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46

Diversity-oriented synthesis of dihydrobenzoxazepinones by coupling the Ugi multicomponent reaction with a Mitsunobu cyclization

• Lisa Moni,
• Luca Banfi,
• Andrea Basso,
• Alice Brambilla and
• Renata Riva

Beilstein J. Org. Chem. 2014, 10, 209–212, doi:10.3762/bjoc.10.16

• isolate the intermediate amine. Since complex amines are often synthesized from the corresponding alcohols via substitution with an azide anion, this one-pot procedure can be useful in further expanding the scope of the Ugi reaction, in addition to the recently reported in situ generation of aldehydes

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• , dihydropyran led instead to the product of C–H perfluoroalkylation β to the oxygen atom [119]. The reaction proceeded in the presence of Zn dust, which was believed to serve as a reductant for the in situ generation of Yb(II) species. The latter would then be able to transfer an electron to the perfluoroalkyl

Self-assembly of 2,3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials

• Valeria C. Edelsztein,
• Andrea S. Mac Cormack,
• Matías Ciarlantini and
• Pablo H. Di Chenna

Beilstein J. Org. Chem. 2013, 9, 1826–1836, doi:10.3762/bjoc.9.213

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

• Ping-An Wang

Beilstein J. Org. Chem. 2013, 9, 1677–1695, doi:10.3762/bjoc.9.192

• -acylaziridine is crucial for the nucleophile attack and the enantioselectivity. It seems that the increase in steric repulsion between nucleophiles and aziridines is helpful to obtain high enantioselectivities of the corresponding products (Figure 10). The desymmetrization of meso-aziridines with the in situ

• generation of carbamodithioic acids from amine and carbon disulfide is also investigated to provide ring-opened products 76 to 80 in high yields and good enantioselectivities (Scheme 11). Chiral 1,2,3-triazolium chlorides Most recently, Ooi [52] and colleagues have described a desymmetrization of meso-N-p

A Lewis acid-promoted Pinner reaction

• Dominik Pfaff,
• Gregor Nemecek and
• Joachim Podlech

Beilstein J. Org. Chem. 2013, 9, 1572–1577, doi:10.3762/bjoc.9.179

• handling of gaseous hydrogen chloride are further drawbacks of this reaction. Nevertheless, milder protocols have developed over the decades: Luo and Jeevanandam used trimethylsilyl chloride (TMSCl) and ethanol for an in situ generation of hydrogen chloride [6]. Watanabe et al. reported on a Pinner

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

• Lucio Melone and
• Carlo Punta

Beilstein J. Org. Chem. 2013, 9, 1296–1310, doi:10.3762/bjoc.9.146

• aerobic oxidation of aldehydes could be performed for the in situ generation of the corresponding peracids in the presence of NHPI, promoting co-oxidative processes catalyzed by PINO. In an early protocol, we reported the NHPI-catalyzed selective aerobic epoxidation of α-olefins and cyclic olefins in the

• /1. These results are objects of two patent applications [60][61]. Light-induced activation The first example of light-induced in situ generation of PINO radical was reported in 2007 by Lucarini and co-workers [62]. Irradiation of N-alkoxyphthalimides with filtered light (λ > 300 nm) from a mercury

Ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene in the presence of aryllithium reagents

• Hao Zhong,
• Jianwu Shi,
• Jianxun Kang,
• Shaomin Wang,
• Xinming Liu and
• Hua Wang

Beilstein J. Org. Chem. 2013, 9, 767–774, doi:10.3762/bjoc.9.87

• work, the metal–halogen exchange of 1-bromopyrene (2i) with n-BuLi or t-BuLi at −78 °C delivered different types of ring-opening products. We believe that the two metal–halogen exchange processes went to complete conversion. The formation of 4 is possibly due to the in situ generation of n-BuBr that is

Intramolecular carbonickelation of alkenes

• Rudy Lhermet,
• Muriel Durandetti and
• Jacques Maddaluno

Beilstein J. Org. Chem. 2013, 9, 710–716, doi:10.3762/bjoc.9.81

• vinylations have been recently reported on activated olefins [14][15]. Some years ago, we showed that the in situ generation of Ni(0) complexes in the presence of both the aromatic halide and the electrophile [16] represents an interesting alternative to electrochemical processes. The main advantages of the

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

• Silvia M. Soria-Castro and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2013, 9, 467–475, doi:10.3762/bjoc.9.50

• catalytic system previously employed (Scheme 2). The use of the polar solvents DMF, MeCN and DMSO gave no conversion at all or yielded only a trace amount of S-phenyl thioacetate (2a) together with Ph2S and Ph2S2 from the in situ generation of benzenethiolate anion (Table 1, entries 1–3). In addition, no

Glycosylation efficiencies on different solid supports using a hydrogenolysis-labile linker

• Mayeul Collot,
• Steffen Eller,
• Markus Weishaupt and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2013, 9, 97–105, doi:10.3762/bjoc.9.13

• -transfer-hydrogenation conditions proved to be very efficient for both deprotection and cleavage of the peptide from the solid support [38]. In this context, in situ generation of palladium black by reduction of palladium(II) acetate with ammonium formate in DMF yielded the best results. Although