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

• organocatalyst forms hydrogen bonds with both H2O2 and cyclic ketones [66]. A chiral Brønsted acid was used as chirality source and activator of H2O2 for an asymmetric sulfoxidation reaction [67] (Scheme 4B). It is generally accepted that in asymmetric Brønsted acid catalysis the activation of both the

• ethanol). Brønsted acid catalysis by TsOH was also employed in a selective sulfoxidation employing PhI(OAc)2 as oxidant [69]. In this case another mode of catalysis was proposed, including the covalent bonding of the acid catalyst anion and the oxidant with the formation of PhI(OTs)OH as the catalytically

Vicinal ketoesters – key intermediates in the total synthesis of natural products

• Marc Paul Beller and
• Ulrich Koert

Beilstein J. Org. Chem. 2022, 18, 1236–1248, doi:10.3762/bjoc.18.129

• intramolecular aldol addition of ketones such as 7 (Scheme 2) [5]. Brønsted-acid catalysis leads via a transition state 8 to the aldol 9, while the use of chelating Lewis acids results via 10 in the epimeric aldol 11. This review is a collection of total syntheses of natural products where vicinal keto esters

Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters

• Jin Yang,
• Dang-Wei Qian and
• Shang-Dong Yang

Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123

• recognized as challenging since there is no single report on such a sequence under Lewis acid catalysis. Herein, we report the synthesis of phosphoric esters by a Lewis acid Cu(OTf)2-catalyzed one-pot Pudovik reaction–phospha-Brook rearrangement sequence between pyridinyl-substituted aldehyde or pyridone

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• reported, by using a metal catalyst or Brønsted-acid catalysis [79][80][81]. However, the efficient regio- and stereoselective installation of the endoperoxide structure is still challenging, because of the increased reactivity of activated oxygen/peroxides and the high sensitivity of peroxide bridges to

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• ) triflate [123], through an adapted Thiele–Winter acetoxylation reaction. The standard procedure involved the use of acetic anhydride and sulfuric acid catalysis. However, the use of sulfuric acid, a strong acid and oxidizing agent, can produce tar in some cases. In order to get around this problem a

A Se···O bonding catalysis approach to the synthesis of calix[4]pyrroles

• Qingzhe Tong,
• Zhiguo Zhao and
• Yao Wang

Beilstein J. Org. Chem. 2022, 18, 325–330, doi:10.3762/bjoc.18.36

• , several synthetic methods to access these compounds have been reported [54][55]. The classical approaches to synthesis of calix[4]pyrrole derivatives mainly involved a stepwise synthesis and Lewis acid as well as Brønsted acid catalysis [54][55]. Notably, a noncovalent catalysis approach to accessing

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• asymmetric addition reaction of racemic naphthylindole 42 with azodicarboxylate 43 under chiral phosphoric acid catalysis. In the presence of CPA 2, 42 and 43 reacted and underwent dynamic kinetic resolution to afford naphthylindoles 44 with axial chirality in moderate to good yields (50–98%) and high

• phosphoric acid catalysis, we developed a highly regio-, diastereo-, and enantioselective dearomatization reaction of 1-substituted 2-naphthols 115 and β,γ-alkynyl-α-imino esters 100. The highly functionalized naphthalenone derivatives 116 with an allene moiety, exhibiting both a quaternary stereocenter and

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

Enantioselective PCCP Brønsted acid-catalyzed aminalization of aldehydes

• Martin Kamlar,
• Robert Reiberger,
• Martin Nigríni,
• Ivana Císařová and
• Jan Veselý

Beilstein J. Org. Chem. 2021, 17, 2433–2440, doi:10.3762/bjoc.17.160

• chiral Brønsted acids. In the scope of Brønsted acid catalysis, chiral phosphoric acids (CPA) are dominating as potent catalysts in various asymmetric transformations [19][20][21][22][23], although the synthesis of these catalysts is expensive and laborious [24]. One of the most frequent examples of CPAs

• strategies employing chiral Brønsted acid catalysis. X-ray single-crystal structure of aminal 3l with the displacement ellipsoids drawn at the 30% probability level. The substrate scope of the aminalization reaction for different aldehydes. aAfter recrystallization; breaction run at 1 mmol scale. The

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• of the glycosidic bond. In this system, the SEE was hydrolytically inactive and the acid catalysis activated the C-1 at the reducing end efficiently to promote chain-elongation. Immobilized catalysis provided cellulose analogues with very high crystallinity. A synthetic mutant enzyme of endoglucanase

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

Methodologies for the synthesis of quaternary carbon centers via hydroalkylation of unactivated olefins: twenty years of advances

• Thiago S. Silva and
• Fernando Coelho

Beilstein J. Org. Chem. 2021, 17, 1565–1590, doi:10.3762/bjoc.17.112

• employed, and an example of a seven-membered lactone was reported (Scheme 25A, 66). However, in the latter case, acid catalysis and reflux were needed to ensure cyclization. Still taking advantage of the enolate intermediate, the Cui group reported the use of olefins 68, containing tethered leaving groups

• reaction was observed in its absence. The authors highlighted the role of the solvent hexafluoro-2-propanol (HFIP) in the stabilization of the radical cation induced by PET and its assistance in the hydrogen shift process. Miscellaneous Lewis acid catalysis in olefin hydroalkylation reactions The ability

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

Valorisation of plastic waste via metal-catalysed depolymerisation

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

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• ]. The remarkable activity was attributed to the dual effect of base and acid catalysis, in addition to the solubility of the catalyst in EG. It is worth mentioning that, in addition to the recovery of chemicals via chemolytic processes, repurposing techniques of PET were developed based on one-pot, two

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

• a longer reaction time, allenes 127 undergo a subsequent intramolecular hydroarylation reaction leading to indenes 128. The authors suggested the formation of FeCl3–HFIP complexes being involved in a Lewis acid-assisted Brønsted acid catalysis. The CF3-substituted propargyl alcohol 129 was found to

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

• there is much progress yet to be made. Brønsted acid catalysis Using chiral amines and NHCs as catalysts to generate asymmetry relies upon the formation of covalently bonded intermediates such as enamines, iminium ions or Breslow intermediates within the catalytic cycle. The first example of merging non

• "Brønsted acid catalysis", yet interestingly their conjugate bases can also be used as efficient hydrogen bonding catalysts. Knowles et al. showed that a tricatalytic system using chiral phosphate 235 can mediate the deracemisation of cyclic urea rac-236 (Scheme 36) [97]. The proposed mechanism involves a

• desired products 267 or 268 in moderate yields and enantioselectivities (3 examples, up to 75:25 er for 267 and 2 examples, up to 68:32 er for 268). Lewis acid catalysis Lewis acids have been known for decades to activate carbonyl compounds through the formation of coordination complexes that increases

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

• catalysis with a second catalytic system has sparked significant interest from the scientific community. Accordingly, numerous unprecedented reactions involving photoredox catalysis in synergy with other activation modes including Brønsted/Lewis acid catalysis, organocatalysis, enzymatic biocatalysis, or

Tuneable access to indole, indolone, and cinnoline derivatives from a common 1,4-diketone Michael acceptor

• Dalel El-Marrouki,
• Sabrina Touchet,
• Abderrahmen Abdelli,
• Hédi M’Rabet,
• Mohamed Lotfi Efrit and
• Philippe C. Gros

Beilstein J. Org. Chem. 2020, 16, 1722–1731, doi:10.3762/bjoc.16.144

• secondary amine and the nonconjugated carbonyl unit. Next, an intramolecular 1,2-addition to the Michael acceptor part of the molecule, previously activated by acid catalysis, takes place (after an imine–enamine equilibrium for the indole pathway), followed by a prototropy, the release of a water molecule

Fluorohydration of alkynes via I(I)/I(III) catalysis

• Jessica Neufeld,
• Constantin G. Daniliuc and
• Ryan Gilmour

Beilstein J. Org. Chem. 2020, 16, 1627–1635, doi:10.3762/bjoc.16.135

• fluorination of acetophenone derivatives was achieved using iodosylarenes and commercially available NEt3/HF 1:5 to generate the ArIF2 species in situ is also highly pertinent [39][40] (Figure 1A). Elegant reports describing the conversion of internal alkynes to α-fluoroketones via π-acid catalysis were also

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

Ferrocenyl-substituted tetrahydrothiophenes via formal [3 + 2]-cycloaddition reactions of ferrocenyl thioketones with donor–acceptor cyclopropanes

• Grzegorz Mlostoń,
• Mateusz Kowalczyk,
• André U. Augustin,
• Peter G. Jones and
• Daniel B. Werz

Beilstein J. Org. Chem. 2020, 16, 1288–1295, doi:10.3762/bjoc.16.109

• by means of spectroscopic methods (R = CF3). In a recent work, an alternative, efficient and useful method for the synthesis of highly functionalized tetrahydrothiophenes of type 6 was reported [9] (Scheme 2). Under Lewis acid catalysis, formal [3 + 2]-cycloadditions of aromatic and cycloaliphatic

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

• Svetlana A. Kuznetsova,
• Alexander S. Gak,
• Yulia V. Nelyubina,
• Vladimir A. Larionov,
• Han Li,
• Michael North,
• Vladimir P. Zhereb,
• Alexander F. Smol'yakov,
• Artem O. Dmitrienko,
• Michael G. Medvedev,
• Igor S. Gerasimov,
• Ashot S. Saghyan and
• Yuri N. Belokon

Beilstein J. Org. Chem. 2020, 16, 1124–1134, doi:10.3762/bjoc.16.99

• ). Both the pH of the medium (specific acid catalysis) and general acid catalysis by the ammonium groups of F-1 were potentially important for the ring opening reactions. The ring openings were conducted in three different media: neat methanol, a mixture of methanol and dichloromethane, and a mixture of

• × 10−2 M in water. Assuming that the average pKa value of the ammonium groups of the protonated form of TAPM was around 4.0, the pH value of the solution would be between 4 and 5. It is therefore most likely that F-1 operated via the general acid catalysis mechanism in this solvent mixture. As the pKa

• value of anilinium cations will only change to a small extent when the solvent is changed from water to methanol, the same general acid catalysis mechanism would be expected to occur in reactions carried out in methanol. For comparison, the commercially available (and most often used heterogeneous

Asymmetric synthesis of CF₂-functionalized aziridines by combined strong Brønsted acid catalysis

• Xing-Fa Tan,
• Fa-Guang Zhang and
• Jun-An Ma

Beilstein J. Org. Chem. 2020, 16, 638–644, doi:10.3762/bjoc.16.60

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

• Katarzyna Włodarczyk,
• Piotr Borowski and
• Marek Stankevič

Beilstein J. Org. Chem. 2020, 16, 88–105, doi:10.3762/bjoc.16.11

• conditions clearly showed that distinct reaction mechanisms were responsible for the substrate’s transformation under Lewis and Brønsted acid catalysis, but both seemed to include the preliminary formation of alkenylphosphine sulfide. This was shown for the Brønsted acid-mediated reaction (Table 4) but

• enantiomerically enriched 53 and 46. Synthesis of substrates for this study. Reaction of β-hydroxyalkylphosphine sulfides with Lewis-acidic AlCl3. Reaction of β-hydroxyalkylphosphine sulfides with Brønsted-acidic H2SO4. Control experiments under Brønsted acid catalysis. Supporting Information Supporting

Bacterial terpene biosynthesis: challenges and opportunities for pathway engineering

• Eric J. N. Helfrich,
• Geng-Min Lin,
• Christopher A. Voigt and
• Jon Clardy

Beilstein J. Org. Chem. 2019, 15, 2889–2906, doi:10.3762/bjoc.15.283

• sesquiterpenes (type I TCs), diterpenes can either be generated by type I TCs or type II TCs [11][55]. Type II TCs initiate carbocation formation by Brønsted acid catalysis to protonate a terminal isoprene double bond or an epoxide ring (Figure 5b) [56]. Thus, cyclization mediated by type II TCs leads to an