Stereoselective mechanochemical synthesis of thiomalonate Michael adducts via iminium catalysis by chiral primary amines

• Michał Błauciak,
• Dominika Andrzejczyk,
• Błażej Dziuk and
• Rafał Kowalczyk

Beilstein J. Org. Chem. 2024, 20, 2313–2322, doi:10.3762/bjoc.20.198

• catalyzed by primary amines in transformation requiring the formation of the imines without catalyst deactivation. The study underscores the potential of mechanochemistry in broadening the scope of organocatalytic and stereoselective transformations including the application of rather unexplored thioesters

Challenge N- versus O-six-membered annulation: FeCl₃-catalyzed synthesis of heterocyclic N,O-aminals

• Giacomo Mari,
• Lucia De Crescentini,
• Gianfranco Favi,
• Fabio Mantellini,
• Diego Olivieri and
• Stefania Santeusanio

Beilstein J. Org. Chem. 2024, 20, 1412–1420, doi:10.3762/bjoc.20.123

• of a high water amount results in catalyst deactivation. Based on these results and what was observed in the optimization tests (Table 1, entry 6), we extended the reaction time but used ACN as solvent, which possesses a higher water content with respect to DCM (experiment C, Scheme 5). Gratifyingly

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• , the presence of the AgNP layer on the cathode caused a decrease of the reaction’s overpotential from –1.66 V to –1.15 V (vs Ag/AgCl), which is thought to prevent catalyst deactivation via successive reduction of the various Ni species, while also avoiding electrode passivation caused by catalyst

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

• bearing indolocarbazole electron donor and benzothienopyrimidine electron acceptor moieties (Figure 14A and B) [72]. In general, three possible pathways can lead to catalyst deactivation and thus, kinetically limit the overall photon economy (Figure 14C, red arrows). Firstly, both photoinduced electron

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• on carbonyl groups resulting in catalyst deactivation. For example, NHPI catalysis is not compatible with primary and secondary amines [75]. To sum up, the future development of N-oxyl radical catalysis is expected to be associated with discoveries of new structural types of N-oxyl radicals with

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• colour of the polymer in the packed bed turned rapidly black (see Supporting Information File 1, Figure S4), and lower yields were observed (Table 1, entries 6 and 7). The catalyst deactivation could be due to the formation of nickel-black [28], or via (photo-)thermal degradation of the polymer. Packed

• packed bed. Together with the catalyst deactivation observed in the temperature study, this result points at a temperature-dependent ligand photodegradation as a likely deactivation mechanism. The amount of nickel leaching observed is significant and, depending on the substrate, the metal contamination

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• could be achieved with high flow rates (125 mL/min; reactor dimensions according to SI: 2 cm diameter and 1 cm height of catalyst filling) in an external electromagnetic field of 28 mT. Heating can be problematic when exothermic reactions are performed. To prevent catalyst deactivation, the group of

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• Sonogashira reaction of iodobenzene derivatives having substituents which can potentially coordinate with iron and consequently cause catalyst deactivation. The efficacy of the coupling is also greatly reliant on the isomer utilized. FeCl2(bdmd) is very compatible with the reactive substrates having para

• recovered and reused, but it could also result in a reduced metal contamination of the products. However, most of the immobilized catalysts suffer from some problems like catalyst deactivation, low turnover numbers, and also leaching of metal. A new heterogeneous cobalt catalyst (Co@imine-porous organic

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

• reoptimised the Schürt’s process for a more general library of molecules (28 compounds were screened) and they managed to overcome the catalyst deactivation enabling a process to be operated continuously for more than 5 days (TOF = 0.09 h−1 and STY = 354 g (L day−1) using a mixture toluene/EtOH 9:1, noticing

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

• Viola Kolaříková,
• Markéta Rybáčková,
• Martin Svoboda and
• Jaroslav Kvíčala

Beilstein J. Org. Chem. 2020, 16, 2757–2768, doi:10.3762/bjoc.16.226

• intermediate to undergo subsequent metathesis reactions leading to catalyst deactivation [23]. In both cases, the effect of ethene was especially productive for the Grubbs 1st generation precatalyst and is typically applied for terminal alkynes or alkynes with little steric hindrance of the triple bond. In

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene–phosphine complexes for the Negishi reaction under flow conditions

• Edgar Peris,
• Raúl Porcar,
• María Macia,
• Jesús Alcázar,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2020, 16, 1924–1935, doi:10.3762/bjoc.16.159

• Organ and co-workers, who have developed silica-immobilized Pd–PEPPSI–IPr–SiO2 [31] and Pd–PEPPSI–IPent–SiO2 [32] catalysts. They observed a gradual catalyst deactivation due to the slow release of palladium over time. However, the high level of catalyst activity, especially for Pd–PEPPSI–IPent–SiO2

• recapture released Pd species) and the top layer with 200 mg of the catalyst 8a (Figure 7a). However, this configuration did not contribute to improve the stability of the system, with a strong catalyst deactivation observed, reaching ca. 47% of the initial activity after 40 h on flow. In an attempt to

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

• Kaj M. van Vliet,
• Nicole S. van Leeuwen,
• Albert M. Brouwer and
• Bas de Bruin

Beilstein J. Org. Chem. 2020, 16, 398–408, doi:10.3762/bjoc.16.38

• acid group seems to be advantageous for the activation of monochloroacetic acid, but the apolar solvent in combination with formation of HCl is likely to cause catalyst deactivation/precipitation. This effect is more pronounced if electron-poor styrenes are used. We also found indications that a

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

• Katharina Hiebler,
• Georg J. Lichtenegger,
• Manuel C. Maier,
• Eun Sung Park,
• Renie Gonzales-Groom,
• Bernard P. Binks and
• Heidrun Gruber-Woelfler

Beilstein J. Org. Chem. 2018, 14, 648–658, doi:10.3762/bjoc.14.52

• initial induction phase (≈30 min) a stable process was achieved, forming the respective products in high yields (up to 99%) for more than 30 h with excellent selectivity without catalyst deactivation [42]. As expected, increasing the catalyst amount and residence time by use of three sequential fixed bed

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

• Carmen Moreno-Marrodan,
• Francesca Liguori and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2017, 13, 734–754, doi:10.3762/bjoc.13.73

• of the desired product are in the range of 95–97%, however, with fast catalyst deactivation due to degradation of the support or sintering of metal particles [129][130]. Reports exist on the partial hydrogenation of 3 under continuous flow. Best results in terms of alkene yield (89%) were reported

• modest yields to 7a (56%), (8a) (21%) and (9a) (21%), eventually with the addition of triethylamine, using a packed-bed multichannel catalytic reactor. The catalyst was based on PdNP onto tri-modal (micro, meso), hierarchical porous synthetic carbon [152]. No catalyst deactivation was detected over 5

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

• concentration of free amine present in the reaction mixture by using the triflate salts of the amines was crucial for obtaining high enantioselectivity. Excess free amine resulted in catalyst deactivation and a racemic background reaction. Electron-rich and neutral aromatic amines added to both acyclic and

Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

• Kevin Lafaye,
• Cyril Bosset,
• Lionel Nicolas,
• Amandine Guérinot and
• Janine Cossy

Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241

• Alkenes containing N-heteroaromatics are known to be poor partners in cross-metathesis reactions, probably due to catalyst deactivation caused by the presence of a nitrogen atom. However, some examples of ring-closing and cross-metathesis involving alkenes that incorporate N-heteroaromatics can be found

• delineate some guidelines for the use of these challenging substrates in metathesis reactions. Keywords: catalyst deactivation; cross-metathesis; N-heteroaromatic; pyridine; ring-closing metathesis; Introduction Over the past decades, metathesis has become a key reaction within the organic chemist’s

• deactivation caused by amino derivatives will be first presented and discussed. RCM and CM involving alkenes possessing N-heteroaromatics will be then successively examined [38]. Review Mechanistic insights into amine-induced catalyst deactivation Recently, intensive studies dealing with ruthenium catalyst

Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

• Hynek Balcar,
• Naděžda Žilková,
• Martin Kubů,
• Michal Mazur,
• Zdeněk Bastl and
• Jiří Čejka

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

• in Table 3. The catalyst was used 5 times without any decrease in the conversion. Due to the very low Ru leaching level (only 0.3% of the original amount of Ru was found in the combined samples from runs 1 to 5), the conversion drop after the fifth run must be ascribed to the catalyst deactivation

Practical synthesis of indoles and benzofurans in water using a heterogeneous bimetallic catalyst

• Cybille Rossy,
• Eric Fouquet and
• François-Xavier Felpin

Beilstein J. Org. Chem. 2013, 9, 1426–1431, doi:10.3762/bjoc.9.160

• separation from the reaction media [23]. We believe that a similar behaviour can explain the catalyst deactivation observed in our studies. The use of flow technology might address this issue as stated by Djakovitch et al., and we are currently investigating this promising alternative. Conclusion In summary

Selective copper(II) acetate and potassium iodide catalyzed oxidation of aminals to dihydroquinazoline and quinazolinone alkaloids

• Matthew T. Richers,
• Chenfei Zhao and
• Daniel Seidel

Beilstein J. Org. Chem. 2013, 9, 1194–1201, doi:10.3762/bjoc.9.135

• , entry 5). A number of different copper salts, solvents and acids were then evaluated, but none of the changes led to a further improvement in yield. It appears that under certain conditions catalyst deactivation via copper oxide formation decreased the catalyst turnover and consequently product yields

Coupled chemo(enzymatic) reactions in continuous flow

• Ruslan Yuryev,
• Simon Strompen and
• Andreas Liese

Beilstein J. Org. Chem. 2011, 7, 1449–1467, doi:10.3762/bjoc.7.169

• ). The coupled reaction is carried out in a continuously operated packed-bed microreactor. As compared to the batch-mode experiments, higher concentrations of H2O2 were applied without detectable catalyst deactivation after 24 hours. At 100% conversion, a space-time yield of 646 g L−1 day−1 was obtained

The catalytic performance of Ru–NHC alkylidene complexes: PCy₃ versus pyridine as the dissociating ligand

• Stefan Krehl,
• Diana Geißler,
• Sylvia Hauke,
• Oliver Kunz,
• Lucia Staude and
• Bernd Schmidt

Beilstein J. Org. Chem. 2010, 6, 1188–1198, doi:10.3762/bjoc.6.136

• slow catalyst deactivation, whereas pyridine complex H showed significantly enhanced activity in acetic acid, with a conversion of 68% after one hour. This result suggests that by switching from toluene to acetic acid the balance of catalyst deactivation and enhanced initiation is shifted to the

• if the pyridine complex H is used as a catalyst. For other examples, we have previously observed that benzyl ether moieties in close proximity to a C–C-multiple bond retard or inhibit metathesis reactions [50]. Presumably, partial catalyst deactivation by coordination of the benzyloxy group to the

From discovery to production: Scale- out of continuous flow meso reactors

• Peter Styring and
• Ana I. R. Parracho

Beilstein J. Org. Chem. 2009, 5, No. 29, doi:10.3762/bjoc.5.29

• study the possibility of catalyst deactivation was considered. However, the fact that steady state production of around 66% over the study up to 31 h would dispel this theory. Indeed ICP-AES studies showed no significant loss of nickel from the catalyst. The likely scenario is that magnesium salts had

A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed- bed microreactor

• Andrew Bogdan and
• D. Tyler McQuade

Beilstein J. Org. Chem. 2009, 5, No. 17, doi:10.3762/bjoc.5.17

• solid-supported catalysis have aimed to solve these issues. Numerous flow oxidations have been presented in the literature [13][14][15][16], however many rely on stoichiometric reagents [17][18], suffer from catalyst deactivation [19][20], or rely on soluble catalysts [21], all of which limit their