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Search for "regiodivergent" in Full Text gives 7 result(s) in Beilstein Journal of Organic Chemistry.
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
Graphical Abstract
Figure 1: Oxidative and reductive activations of organic compounds harvesting photoredox catalysis.
Figure 2: General catalytic cycles of radical ion conPET (left) and radical ion e-PRC (right).
Figure 3: “Beginner’s guide”: comparison between advantages, capacities, and prospectives of conPET and PEC.
Figure 4: A) conPET reductive dehalogenation of aryl halides with PDI. B) Reductive C–H arylation with pyrrol...
Figure 5: A) Chromoselective mono- and disubstitution or polybrominated pyrimidines with pyrroles. B) Sequent...
Figure 6: A) Synthesis of pyrrolo[1,2-a]quinolines. B) Synthesis of ullazines.
Figure 7: A) Reductive phosphorylation of aryl halides via conPET. B) Selected examples from the substrate sc...
Figure 8: A) Reductive dehalogenation of aryl halides via conPET and selected examples from the substrate sco...
Figure 9: A) Reductive C–H arylation of aryl halides via conPET (top) and selected examples from the substrat...
Figure 10: A) Reductive hydrodehalogenation of aryl halides with Mes-Acr-BF4. B) Selected examples from the su...
Figure 11: A) Reductive hydrodechlorination of aryl chlorides with 4-DPAIPN. B) Proposed formation of CO2•−. C...
Figure 12: A) Reductive conPET borylation with 3CzEPAIPN (top) and selected examples from the substrate scope ...
Figure 13: Scale-up of conPET phosphorylation with 3CzEPAIPN.
Figure 14: A) Borylation of 1d. B) Characteristics and structure of PC1 with green and red parts showing the l...
Figure 15: A) Reductive C–H arylation scope with polysulfide conPET (top) and selected examples from the subst...
Figure 16: Scale-up of A) C–H arylation and B) dehaloborylation with polysulfide photocatalysis in continuous-...
Figure 17: A) Formation of [Ir1]0 and [Ir2]0 upon PET between [Ir1]+ and Et3N. B) Mechanism of multi-photon ta...
Figure 18: A) Reductive hydrodehalogenation of aryl halides via multi-photon tandem photocatalysis. B) Selecte...
Figure 19: A) Carbonylative amidation of aryl halides in continuous flow. B) Selected examples from the substr...
Figure 20: A) General scheme for reductive (RQ) and oxidative quenching (OQ) protocols using [FeIII(btz)3](PF6)...
Figure 21: A) Carbonylative amidation of alkyl iodides with [IrIII(ppy)2(dtbbpy)]PF6. B) Selected examples fro...
Figure 22: A) Carboxylative C–N bond cleavage in cyclic amines. B) Selected examples from the substrate scope....
Figure 23: A) Formal reduction of alkenes to alkanes via transfer hydrogenation. B) Selected examples from the...
Figure 24: A) Birch-type reduction of benzenes with PMP-BPI. B) Selected examples from the substrate scope (sc...
Figure 25: Proposed mechanism of the OH− mediated conPET Birch-type reduction of benzene via generation of sol...
Figure 26: Reductive detosylation of N-tosylated amides with Mes-Acr-BF4. B) Selected examples from the substr...
Figure 27: A) Reductive detosylation of N-tosyl amides by dual PRC. B) Selected examples from the substrate sc...
Figure 28: A) Mechanism of the dual PRC based on PET between [Cu(dap)2]+ and DCA. B) Mechanism of the dual PRC...
Figure 29: A) N–O bond cleavage in Weinreb amides with anthracene. B) N–O bond cleavage in Weinreb amides rely...
Figure 30: A) Pentafluorosulfanylation and fluoride elimination. B) Mechanism of the pentafluorosulfanylation ...
Figure 31: A) α-Alkoxypentafluorosulfanylation (top) and selected examples from the substrate scope (bottom). ...
Figure 32: A) Oxidative amination of arenes with azoles catalyzed by N-Ph PTZ. B) Selected examples from the s...
Figure 33: A) C(sp3)–H bond activation by HAT via chloride oxidation by *N-Ph PTZ•+. B) Proposed mechanism for...
Figure 34: A) Recycling e-PRC C–H azolation of electron-rich arenes with pyrazoles using Mes-Acr+ as a photoca...
Figure 35: A) Radical ion e-PRC direct oxidation of unactivated arenes using TAC+ as an electro-activated phot...
Figure 36: A) Radical ion e-PRC direct oxidation of unactivated arenes using TPA as an electro-activated photo...
Figure 37: Proposed mechanism (top) and mode of preassembly (bottom).
Figure 38: A) Possible preassemblies of reactive (left) vs unreactive (right) arenes. B) Calculated spin densi...
Figure 39: A) Recycling e-PRC C(sp2 )–H acetoxylation of arenes using DDQ as a photocatalyst. B) Proposed cata...
Figure 40: Gram scale hydroxylation of benzene in a recirculated flow setup.
Figure 41: A) Radical ion e-PRC vicinal diamination of alkylarenes using TAC+ as an electro-activated photocat...
Figure 42: A) Sequential oxygenation of multiple adjacent C–H bonds under radical ion e-PRC using TAC+ as an e...
Figure 43: A) Enantioselective recycling e-PRC cyanation of benzylic C–H bonds using ADQS as photocatalyst. B)...
Figure 44: Proposed tandem mechanism by Xu and co-workers.
Figure 45: A) Enantioselective recycling e-PRC decarboxylative cyanation using Cu(acac)2, Ce(OTf)3 and a box l...
Figure 46: A) Enantioselective recycling e-PRC benzylic cyanation using Cu(MeCN)4BF4, box ligand and anthraqui...
Figure 47: A) Radical ion e-PRC acetoxyhydroxylation of aryl olefins using TAC+ as an electro-activated photoc...
Figure 48: Selected examples from the substrate scope.
Figure 49: Photoelectrochemical acetoxyhydroxylation in a recirculated flow setup.
Figure 50: A) Radical ion e-PRC aminooxygenation of aryl olefins using TAC+ as an electro-activated photocatal...
Figure 51: A) Recycling e-PRC C–H alkylation of heteroarenes with organic trifluoroborates using Mes-Acr+ as p...
Figure 52: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using CeCl3·7H2O as catalyst. B) ...
Figure 53: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using Fe(NH4)2(SO4)2·6H2O as cata...
Figure 54: A) Recycling e-PRC C–H alkylation of heteroarenes with alkyl oxalates and 4CzIPN as photocatalyst. ...
Figure 55: A) Recycling e-PRC decarboxylative C–H carbamoylation of heteroarenes using 4CzIPN as photocatalyst...
Figure 56: A) Photoelectrochemical HAT-mediated hydrocarbon activation via the chlorine radical. B) Proposed m...
Figure 57: A) Selected examples from the substrate scope. B) Gram and decagram scale semi-continuous flow PEC ...
Figure 58: A) Photoelectrochemical HAT-mediated dehydrogenative coupling of benzothiazoles with aliphatic C–H ...
Figure 59: A) Photoelectrochemical HAT activation of ethers using electro-activated TAC+ as photocatalyst. B) ...
Figure 60: Selected examples from the substrate scope.
Figure 61: A) Photoelectrochemical HAT-mediated synthesis of alkylated benzimidazo-fused isoquinolinones using...
Figure 62: A) Decoupled photoelectrochemical cerium-catalyzed oxydichlorination of alkynes using CeCl3 as cata...
Figure 63: Proposed decoupled photoelectrochemical mechanism.
Figure 64: A) Decoupled photoelectrochemical ring-opening bromination of tertiary cycloalkanols using MgBr2 as...
Figure 65: A) Recycling e-PRC ring-opening functionalization of cycloalkanols using CeCl3 as catalyst. B) Prop...
Figure 66: Selected examples from the substrate scope of the PEC ring-opening functionalization.
Figure 67: A) Radical ion e-PRC reduction of chloro- and bromoarenes using DCA as catalyst and various accepto...
Figure 68: A) Screening of different phthalimide derivatives as catalyst for the e-PRC reduction of aryl halid...
Figure 69: Screening of different organic catalysts for the e-PRC reduction of trialkylanilium salts.
Figure 70: A) e-PRC reduction of phosphonated phenols and anilinium salts. B) Selected examples from the subst...
Figure 71: A) ConPET and e-PRC reduction of 4-bromobenzonitrile using a naphthalene diimide (NDI) precatalyst ...
Figure 72: A) Radical ion e-PRC reduction of phosphinated aliphatic alcohols with n-BuO-NpMI as catalyst. B) C...
Figure 73: Selected examples from the substrate scope.
Figure 74: A) Recycling e-PRC reductive dimerization of benzylic chlorides using a [Cu2] catalyst. B) Proposed...
Figure 75: A) Decoupled photoelectrochemical C–H alkylation of heteroarenes through deamination of Katritzky s...
Figure 76: Proposed mechanism by Chen and co-workers.
Regiodivergent synthesis of functionalized pyrimidines and imidazoles through phenacyl azides in deep eutectic solvents
- Paola Vitale,
- Luciana Cicco,
- Ilaria Cellamare,
- Filippo M. Perna,
- Antonio Salomone and
- Vito Capriati
Beilstein J. Org. Chem. 2020, 16, 1915–1923, doi:10.3762/bjoc.16.158
- , Università del Salento, Prov.le Lecce-Monteroni, 73100 Lecce, Italy Dipartimento di Chimica, Università di Bari “Aldo Moro”, Via E. Orabona 4, I-70125 Bari, Italy 10.3762/bjoc.16.158 Abstract We report that phenacyl azides are key compounds for a regiodivergent synthesis of valuable, functionalized
Graphical Abstract
Scheme 1: One-pot synthesis of 2,5-diarylpyrazines (A) (path a) or 2-aroyl-(4 or 5)-aryl-(1H)-imidazoles (B) ...
Scheme 2: Transformation of phenacyl bromide (1a) in ChCl/Gly into phenacyl azide (2a) and 2-benzoyl-(4 or 5)...
Scheme 3: Synthesis of 2-aroyl-(4 or 5)-aryl-(1H)-imidazoles 3. Scope of the reaction. Typical conditions: 1 ...
Scheme 4: Proposed mechanism for the formation of 2-aroyl-(4 or 5)-aryl-(1H)-imidazoles 3/3' from α-phenacyl ...
Scheme 5: Proposed mechanism for the formation of 2-benzoyl-(4 or 5)-phenyl-(1H)-imidazoles 3a/3a' and 2,4-di...
Scheme 6: Scope of the synthesis of 2,4-diaroyl-6-arylpyrimidines 7. Typical conditions: 2 (0.3 mmol), Et3N (...
Facile regiodivergent synthesis of spiro pyrrole-substituted pseudothiohydantoins and thiohydantoins via reaction of [e]-fused 1H-pyrrole-2,3-diones with thiourea
- Aleksandr I. Kobelev,
- Nikita A. Tretyakov,
- Ekaterina E. Stepanova,
- Maksim V. Dmitriev,
- Michael Rubin and
- Andrey N. Maslivets
Beilstein J. Org. Chem. 2019, 15, 2864–2871, doi:10.3762/bjoc.15.280
Graphical Abstract
Figure 1: Hydantoin-based commercially available drugs.
Scheme 1: Pseudothiohydantoin–thiohydantoin rearrangement.
Scheme 2: Syntheses of regioisomeric 5-spiro-substituted thiohydantoins and pseudothiohydantoins: previous [10] a...
Figure 2: Electrophilic centers of FPDs 1, starting materials of this study.
Scheme 3: Cyclocondensation of FPDs 1 with 1,3-binucleophilic reagents, resulting in pyrrole-2-one-bearing sp...
Scheme 4: Reaction of FPD 1a with thiourea.
Scheme 5: PTR of 3a to 2a.
Scheme 6: Pathways for the formation of compound 2a.
Scheme 7: Reaction of FPD 1a with monosubstituted thioureas.
Scheme 8: Reaction of FPDs 1 with 1,3-dibutylthiourea at room temperature.
Scheme 9: Plausible PTR pathways.
Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source
- Tetsuaki Fujihara and
- Yasushi Tsuji
Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221
- regiodivergent carboxylation of allyl acetates in the presence of Mn as the reductant [26]. Mita and Sato found that Pd-catalyzed carboxylation of allylic alcohols proceeded using Et2Zn as the reducing agent [27]. The carboxylation of propargyl chloride was reported as one of the examples concerning the Ni
Graphical Abstract
Scheme 1: Optimization of the Co-catalyzed carboxylation of 1a.
Scheme 2: Co-catalyzed carboxylation of propargyl acetates 1.
Scheme 3: Plausible reaction mechanism for the Co-catalyzed carboxylation of propargyl acetates 1.
Scheme 4: Optimization of the Co-catalyzed carboxylation of 3a.
Scheme 5: Co-catalyzed carboxylation of vinyl triflates 3.
Scheme 6: Co-catalyzed carboxylation of a sterically hindered aryl triflate 5.
Scheme 7: Optimization of the Co-catalyzed carboxylation of 7a.
Scheme 8: Scope of the reductive carboxylation of α,β-unsaturated nitriles 7.
Scheme 9: Scope of the carboxylation of α,β-unsaturated carboxamides 9.
Scheme 10: Optimization of the Co-catalyzed carboxylation of 11a.
Scheme 11: Scope of the carboxylation of allylarenes 11.
Scheme 12: Scope of the carboxylation of 1,4-diene derivatives 14.
Scheme 13: Plausible reaction mechanism for the Co-catalyzed C(sp3)–H carboxylation of allylarenes.
Scheme 14: Optimization of the Co-catalyzed carboxyzincation of 16a.
Scheme 15: Derivatization of the carboxyzincated product.
Scheme 16: Co-catalyzed carboxyzincation of alkynes 16.
Scheme 17: Plausible reaction mechanism for the Co-catalyzed carboxyzincation of alkynes 16.
Scheme 18: Co-catalyzed four-component coupling of alkynes 16, acrylates 18, CO2, and zinc.
Scheme 19: Proposed reaction mechanism for the Co-catalyzed four-component coupling.
Scheme 20: Visible-light-driven hydrocarboxylation of alkynes.
Scheme 21: Visible-light-driven synthesis of γ-hydroxybutenolides from ortho-ester-substituted aryl alkynes.
Scheme 22: One-pot synthesis of coumarines and 2-quinolones via hydrocarboxylation/alkyne isomerization/cycliz...
Scheme 23: Proposed reaction mechanism for the Co-catalyzed carboxylative cyclization of ortho-substituted aro...
Scheme 24: Rh-catalyzed carboxylation of arylboronic esters 25.
Scheme 25: Rh-catalyzed carboxylation of alkenylboronic esters 27.
Scheme 26: Plausible reaction mechanism for the Rh-catalyzed carboxylation of arylboronic esters 25.
Scheme 27: Ligand effect on the Rh-catalyzed carboxylation of 2-phenylpyridine 29a.
Scheme 28: Rh-catalyzed chelation-assisted C(sp2)–H bond carboxylation with CO2.
Scheme 29: Reaction mechanism for the Rh-catalyzed C(sp2)–H carboxylation of 2-pyridylarenes 29.
Scheme 30: Carboxylation of C(sp2)–H bond with CO2.
Scheme 31: Carboxylation of C(sp2)–H bond with CO2.
Scheme 32: Reaction mechanism for the Rh-catalyzed C(sp2)–H carboxylation of 2-arylphenols 34.
Scheme 33: Hydrocarboxylation of styrene derivatives with CO2.
Scheme 34: Hydrocarboxylation of α,β-unsaturated esters with CO2.
Scheme 35: Asymmetric hydrocarboxylation of α,β-unsaturated esters with CO2.
Scheme 36: Proposed reaction mechanism for the Rh-catalyzed hydrocarboxylation of C–C double bonds with CO2.
Scheme 37: Visible-light-driven hydrocarboxylation with CO2.
Scheme 38: Visible-light-driven Rh-catalyzed hydrocarboxylation of C–C double bonds with CO2.
Scheme 39: Optimization of reaction conditions on the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne 42a and ...
Scheme 40: [2 + 2 + 2] Cycloaddition of diyne and CO2.
Scheme 41: Proposed reaction pathways for the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne and CO2.
Rhodium-catalyzed C–H functionalization of heteroarenes using indoleBX hypervalent iodine reagents
- Erwann Grenet,
- Ashis Das,
- Paola Caramenti and
- Jérôme Waser
Beilstein J. Org. Chem. 2018, 14, 1208–1214, doi:10.3762/bjoc.14.102
- nitrogen and a transition metal catalyst (reaction 1, Scheme 1A) [11][12][13][14][15][16][17][18][19]. In particular, Li and co-workers have used ethynylbenziodoxolone (EBX) hypervalent iodine reagents to achieve a regiodivergent alkynylation of the pyridinone core employing either a gold(I) or a rhodium
Graphical Abstract
Figure 1: Bioactive compounds with pyridinone, quinolone and indole cores.
Scheme 1: C–H functionalization of pyridinones and quinoline N-oxides.
Scheme 2: Scope and limitations of the Rh-catalyzed C–H activation of [1,2'-bipyridin]-2-one.
Scheme 3: Scope of the Rh-catalyzed peri C–H activation of quinoline N-oxides.
Scheme 4: Product modifications.
Reagent-controlled regiodivergent intermolecular cyclization of 2-aminobenzothiazoles with β-ketoesters and β-ketoamides
- Irwan Iskandar Roslan,
- Kian-Hong Ng,
- Gaik-Khuan Chuah and
- Stephan Jaenicke
Beilstein J. Org. Chem. 2017, 13, 2739–2750, doi:10.3762/bjoc.13.270
- Irwan Iskandar Roslan Kian-Hong Ng Gaik-Khuan Chuah Stephan Jaenicke Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 10.3762/bjoc.13.270 Abstract Two regiodivergent approaches to intermolecular cyclization of 2-aminobenzothiazoles with β-ketoesters
- , In(OTf)3, results in the regioselective nucleophilic attack at both carbonyl groups forming benzo[4,5]thiazolo[3,2-a]pyrimidin-4-ones instead. Keywords: cyclization; fused-ring systems; indium; radical; regiodivergent; Introduction β-Ketoesters are versatile substrates frequently used in
- developed two regiodivergent protocols for the intermolecular cyclization of 2-aminobenzothiazoles with β-ketoesters and β-ketoamides that are determined by the reagents used. This is possible due to the versatility of β-ketoesters in switching polarities and reactivities in the presence of different
Graphical Abstract
Scheme 1: Two different intermolecular cyclization pathways controlled by reagents used.
Scheme 2: Scope of reaction. Reaction conditions: 1 (1.2 mmol), 2 (1.0 mmol), KOt-Bu (2 mmol), in 3 mL CBrCl3...
Scheme 3: Scope of the reaction. Reaction conditions: 1 (1.0 mmol), 2 (1.5 mmol), In(OTf)3 (0.1 mmol), in 1.5...
Scheme 4: Control experiments.
Figure 1: Proposed mechanism (benzo[d]imidazo[2,1-b]thiazoles).
Figure 2: Proposed mechanism (benzo[4,5]thiazolo[3,2-a]pyrimidin-4-ones).
Regiodivergent condensation of 5-alkoxycarbonyl-1H-pyrrol-2,3-diones with cyclic ketazinones en route to spirocyclic scaffolds
- Alexey Yu. Dubovtsev,
- Maksim V. Dmitriev,
- Аndrey N. Maslivets and
- Michael Rubin
Beilstein J. Org. Chem. 2017, 13, 2179–2185, doi:10.3762/bjoc.13.218
- in the target-oriented synthesis of pyrrole-based natural alkaloids [34][35][36][37][38]. Herein we wish to report a new synthetic route towards spirocyclic scaffolds possessing partially hydrogenated indole or benzofuran cores. The featured approach is based on the highly efficient regiodivergent
- -methanobenzo[f][1,3]oxazepines. We also found efficient regiodivergent spirocondensation of the same pyrrolediones with cyclic ketazinones affording the formation of spirocyclic scaffolds with either hydroindoles or hydrobenzofuran moieties. Remarkably, the direction of this condensation can be efficiently
Graphical Abstract
Scheme 1: Spirocyclization of enamines with 5-methoxycarbonyl-1H-pyrrolediones.
Scheme 2: Non-catalyzed spirocyclization of enoles (vinylogous carbonates and carbamates) with 5-methoxycarbo...
Scheme 3: Acid-catalyzed spirocyclization of enoles (vinylogous carboxylates) with 5-alkoxycarbonyl-1H-pyrrol...
Figure 1: ORTEP drawing of compound 12ab (CCDC 1546062) showing 50% probability amplitude displacement ellips...
Scheme 4: Formation of mono-imines and mono-hydrazones of 1,3-cyclohexanediones and tautomeric equilibrium be...
Scheme 5: Spirocyclizations involving non-bulky ketazinones 17 and 5-alkoxycarbonyl-1H-pyrrolediones 9.
Figure 2: ORTEP drawing of compound 21ab (CCDC 1546063) showing 50% probability amplitude displacement ellips...
Figure 3: ORTEP drawing of compound 22a (CCDC 1546065) showing 50% probability amplitude displacement ellipso...
Scheme 6: Spirocyclizations involving bulky ketazinones 22 and 5-alkoxycarbonyl-1H-pyrrolediones 9.
Figure 4: ORTEP drawing of compound 23aa (CCDC 1546064) showing 50% probability amplitude displacement ellips...
