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

Thioester derivatives of the natural product psammaplin A as potent histone deacetylase inhibitors

• Matthias G. J. Baud,
• Thomas Leiser,
• Vanessa Petrucci,
• Mekala Gunaratnam,
• Stephen Neidle,
• Franz-Josef Meyer-Almes and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2013, 9, 81–88, doi:10.3762/bjoc.9.11

• explanations could be envisaged to explain this result: (1) The thioester is stable to the assay buffer and therefore does not contribute to the in situ generation of the free thiol. (2) The quantity of free thiol generated in situ in this experiment was too low to be quantified. An alternative hypothesis for

Flow photochemistry: Old light through new windows

• Jonathan P. Knowles,
• Luke D. Elliott and
• Kevin I. Booker-Milburn

Beilstein J. Org. Chem. 2012, 8, 2025–2052, doi:10.3762/bjoc.8.229

N-Heterocyclic carbene-catalyzed direct cross-aza-benzoin reaction: Efficient synthesis of α-amino-β-keto esters

• Takuya Uno,
• Yusuke Kobayashi and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2012, 8, 1499–1504, doi:10.3762/bjoc.8.169

• employing the imines directly has rarely been developed [40][42], due to the unproductive reaction of NHCs with the imines. Therefore, in situ generation of imines or iminium ions from their precursors is generally required to control their reactivity. We anticipated that the introduction of appropriate

Synthesis of new pyrrole–pyridine-based ligands using an in situ Suzuki coupling method

• Matthias Böttger,
• Björn Wiegmann,
• Steffen Schaumburg,
• Peter G. Jones,
• Wolfgang Kowalsky and
• Hans-Hermann Johannes

Beilstein J. Org. Chem. 2012, 8, 1037–1047, doi:10.3762/bjoc.8.116

• ; in situ generation; pyrrole-pyridine; Suzuki coupling; Introduction Tridentate ligands have recently received attention in the area of rare-earth-metal complex chemistry [1][2][3][4][5]. Many rare-earth-metal cations, such as europium(III), have the tendency to be nine-coordinating species. Besides

Hybrid super electron donors – preparation and reactivity

• Jean Garnier,
• Douglas W. Thomson,
• Shengze Zhou,
• Phillip I. Jolly,
• Leonard E. A. Berlouis and
• John A. Murphy

Beilstein J. Org. Chem. 2012, 8, 994–1002, doi:10.3762/bjoc.8.112

• donor as 4, while the transfer of the second electron occurs at a more negative potential than for the first electron from 1. In situ generation of 9 from 20 (1.5 equiv, Scheme 3) and reaction with iodoarenes 28 and 30 was again carried out at room temperature. As for the reactions with donor 11, the

Efficient oxidation of oleanolic acid derivatives using magnesium bis(monoperoxyphthalate) hexahydrate (MMPP): A convenient 2-step procedure towards 12-oxo-28-carboxylic acid derivatives

• Jorge A. R. Salvador,
• Vânia M. Moreira,
• Rui M. A. Pinto,
• Ana S. Leal and
• José A. Paixão

Beilstein J. Org. Chem. 2012, 8, 164–169, doi:10.3762/bjoc.8.17

• -carboxylic acid 11 was obtained, in 85% yield, after the typical work-up procedure [18]. The formation of compound 11 from the 12α-hydroxy-28,13β-olide 2 is likely to occur due to the in situ generation of a Brønsted acid species from bismuth(III) triflate, which promotes ring opening of the 28,13β-olide

A general and facile one-pot process of isothiocyanates from amines under aqueous conditions

• Nan Sun,
• Bin Li,
• Jianping Shao,
• Weimin Mo,
• Baoxiang Hu,
• Zhenlu Shen and
• Xinquan Hu

Beilstein J. Org. Chem. 2012, 8, 61–70, doi:10.3762/bjoc.8.6

• Academy of Sciences, Lanzhou 730000, China 10.3762/bjoc.8.6 Abstract A general and facile one-pot protocol for the preparation of a broad range of alkyl and aryl isothiocyanates has been developed from their corresponding primary amines under aqueous conditions. This synthetic process involves an in situ

• generation of a dithiocarbamate salt from the amine substrate by reacting with CS2 followed by elimination to form the isothiocyanate product with cyanuric acid as the desulfurylation reagent. The choice of solvent is of decisive importance for the successful formation of the dithiocarbamate salt

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• particularly alkynones. In situ generation of the latter is an interesting means of overcoming the poor commercial availability of these compounds and also offers the flexibility needed for library production (Scheme 15). Thus various (hetero)aryl acid chlorides and terminal alkynes were heated in THF in the

PEG-embedded KBr₃: A recyclable catalyst for multicomponent coupling reaction for the efficient synthesis of functionalized piperidines

• Sanny Verma,
• Suman L. Jain and
• Bir Sain

Beilstein J. Org. Chem. 2011, 7, 1334–1341, doi:10.3762/bjoc.7.157

• , safer handling and efficient recycling of the catalyst make this more suitable and preferable than the existing organic ammonium tribromides [30][31]. The mechanism of this reaction is not clear at this stage, however, the reaction probably involves the in situ generation of HBr in the presence of

• reaction mixture by UV–vis spectroscopy at the end of the reaction; no bromine was detected in the reaction mixture, thus establishing the in situ generation of bromine from the reagent during the reaction. Conclusion In summary, we have described the first time use of inexpensive, environmentally benign

• bromine could be detected in the reaction mixture as analyzed by UV−vis spectroscopy; this established the in situ generation of bromine from the reagent during the reaction. Typical experimental procedure Into a stirred mixture of aniline (0.2 g, 2.15 mmol), benzaldehyde (0.2 g, 1.89 mmol), ethyl

Functionalization of heterocyclic compounds using polyfunctional magnesium and zinc reagents

• Paul Knochel,
• Matthias A. Schade,
• Sebastian Bernhardt,
• Georg Manolikakes,
• Albrecht Metzger,
• Fabian M. Piller,
• Christoph J. Rohbogner and
• Marc Mosrin

Beilstein J. Org. Chem. 2011, 7, 1261–1277, doi:10.3762/bjoc.7.147

• -catalyzed cross-coupling of benzylic zinc reagent 34 with ethyl 2-chloronicotinate. In situ generation of arylzinc reagents using Mg in the presence of LiCl and ZnCl2. Zincation of heterocycles with TMP2Zn (42). Preparation of highly functionalized zincated heterocycles using TMP2Zn·2MgCl2·2LiCl (42