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Search for "cinnamyl alcohol" in Full Text gives 16 result(s) in Beilstein Journal of Organic Chemistry.
Recent advances in synthetic approaches for bioactive cinnamic acid derivatives
- Betty A. Kustiana,
- Galuh Widiyarti and
- Teni Ernawati
Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85
- with nucleophilic cinnamonitrile 149 to give benzocyclooctene 150 via iodonium intermediate 151 (Scheme 46) [86]. 2.2 Oxidative acylations Cinnamic ester or amide preparation could also be achieved by oxidizing cinnamyl alcohol, aldehyde, imine, and ketone as an alternative to the traditional O/N
- ]. A similar reaction, reported by Zheng and co-workers (2020) utilized a graphene-supported Au/Pd catalyst to achieve the aerobic oxidative esterification of cinnamyl alcohol 157 via oxidation of the hemiacetal embedded in the catalyst surface 158 to obtain the corresponding ester 44 in quantitative
- yield (Scheme 48B) [89]. Furthermore, Doris and co-workers (2019) also utilized a Au catalyst for oxidative esterification reactions. Herein, Au nanoparticles supported on carbon nanotubes (AuCNT) catalyzed the conversion of cinnamyl alcohol 157 to the corresponding ester 44 via hemiacetal-anchored on
Graphical Abstract
Figure 1: Biologically active cinnamic acid derivatives.
Scheme 1: General synthetic strategies for cinnamic acid derivatizations.
Scheme 2: Cinnamic acid coupling via isobutyl anhydride formation.
Scheme 3: Amidation reaction via O/N-pivaloyl activation.
Scheme 4: Cinnamic acid amidation using TCCA/PPh3 reagent.
Scheme 5: Cinnamic acid amidation using triazine-based reagents.
Scheme 6: Cinnamic acid amidation using continuous flow mechanochemistry.
Scheme 7: Cinnamic acid amidation using COMU as coupling reagent.
Scheme 8: Cinnamic acid amidation using allenone coupling reagent.
Scheme 9: Cinnamic acid amidation using 4-acetamidophenyl triflimide as reagent.
Scheme 10: Cinnamic acid amidation using methyltrimethoxysilane (MTM).
Scheme 11: Cinnamic acid amidation utilizing amine–borane reagent.
Scheme 12: Cinnamic acid amidation using TCCA/PPh3 reagent.
Scheme 13: Cinnamic acid amidation using PPh3/I2 reagent.
Scheme 14: Cinnamic acid amidation using PCl3 reagent.
Scheme 15: Cinnamic acid amidation utilizing pentafluoropyridine (PFP) as reagent.
Scheme 16: Cinnamic acid amidation using hypervalent iodine(III).
Scheme 17: Mechanochemical amidation using 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) reagent.
Scheme 18: Methyl ester preparation using tris(2,4,6-trimethoxyphenyl)phosphine (TMPP).
Scheme 19: N-Trifluoromethyl amide preparation using isothiocyanate and AgF.
Scheme 20: POCl3-mediated amide coupling of carboxylic acid and DMF.
Scheme 21: O-Alkylation of cinnamic acid using alkylating agents.
Scheme 22: Glycoside preparation via Mitsunobu reaction.
Scheme 23: O/N-Acylation via rearrangement reactions.
Scheme 24: Amidation reactions using sulfur-based alkylating agents.
Scheme 25: Amidation reaction catalyzed by Pd0 via C–N cleavage.
Scheme 26: Amidation reaction catalyzed by CuCl/PPh3.
Scheme 27: Cu(II) triflate-catalyzed N-difluoroethylimide synthesis.
Scheme 28: Cu/Selectfluor-catalyzed transamidation reaction.
Scheme 29: CuO–CaCO3-catalyzed amidation reaction.
Scheme 30: Ni-catalyzed reductive amidation.
Scheme 31: Lewis acidic transition-metal-catalyzed O/N-acylations.
Scheme 32: Visible-light-promoted amidation of cinnamic acid.
Scheme 33: Sunlight/LED-promoted amidation of cinnamic acid.
Scheme 34: Organophotocatalyst-promoted N–O cleavage of Weinreb amides to synthesize primary amides.
Scheme 35: Cinnamamide synthesis through [Ir] photocatalyst-promoted C–N-bond cleavage of tertiary amines.
Scheme 36: Blue LED-promoted FeCl3-catalyzed reductive transamidation.
Scheme 37: FPyr/TCT-catalyzed amidation of cinnamic acid derivative 121.
Scheme 38: Cs2CO3/DMAP-mediated esterification.
Scheme 39: HBTM organocatalyzed atroposelective N-acylation.
Scheme 40: BH3-catalyzed N-acylation reactions.
Scheme 41: Borane-catalyzed N-acylation reactions.
Scheme 42: Catalytic N-acylation reactions via H/F bonding activation.
Scheme 43: Brønsted base-catalyzed synthesis of cinnamic acid esters.
Scheme 44: DABCO/Fe3O4-catalyzed N-methyl amidation of cinnamic acid 122.
Scheme 45: Catalytic oxidation reactions of acylating agents.
Scheme 46: Preparation of cinnamamide-substituted benzocyclooctene using I(I)/I(III) catalysis.
Scheme 47: Pd-colloids-catalyzed oxidative esterification of cinnamyl alcohol.
Scheme 48: Graphene-supported Pd/Au alloy-catalyzed oxidative esterification via hemiacetal intermediate.
Scheme 49: Au-supported on A) carbon nanotubes (CNT) and B) on porous boron nitride (pBN) as catalyst for the ...
Scheme 50: Cr-based catalyzed oxidative esterification of cinnamyl alcohols with H2O2 as the oxidant.
Scheme 51: Co-based catalysts used for oxidative esterification of cinnamyl alcohol.
Scheme 52: Iron (A) and copper (B)-catalyzed oxidative esterification of cinnamaldehyde.
Scheme 53: NiHPMA-catalyzed oxidative esterification of cinnamaldehyde.
Scheme 54: Synthesis of cinammic acid esters through NHC-catalyzed oxidative esterification via intermolecular...
Scheme 55: Redox-active NHC-catalyzed esterification via intramolecular oxidation.
Scheme 56: Electrochemical conversion of cinnamaldehyde to methyl cinnamate.
Scheme 57: Bu4NI/TBHP-catalyzed synthesis of bisamides from cinnamalaldehyde N-tosylhydrazone.
Scheme 58: Zn/NC-950-catalyzed oxidative esterification of ketone 182.
Scheme 59: Ru-catalyzed oxidative carboxylation of terminal alkenes.
Scheme 60: Direct carboxylation of alkenes using CO2.
Scheme 61: Carboxylation of alkenylboronic acid/ester.
Scheme 62: Carboxylation of gem-difluoroalkenes with CO2.
Scheme 63: Photoredox-catalyzed carboxylation of difluoroalkenes.
Scheme 64: Ru-catalyzed carboxylation of alkenyl halide.
Scheme 65: Carboxylation of alkenyl halides under flow conditions.
Scheme 66: Cinnamic acid ester syntheses through carboxylation of alkenyl sulfides/sulfones.
Scheme 67: Cinnamic acid derivatives synthesis through a Ag-catalyzed decarboxylative cross-coupling proceedin...
Scheme 68: Pd-catalyzed alkyne hydrocarbonylation.
Scheme 69: Fe-catalyzed alkyne hydrocarbonylation.
Scheme 70: Alkyne hydrocarboxylation using CO2.
Scheme 71: Alkyne hydrocarboxylation using HCO2H as CO surrogate.
Scheme 72: Co/AlMe3-catalyzed alkyne hydrocarboxylation using DMF.
Scheme 73: Au-catalyzed oxidation of Au–allenylidenes.
Scheme 74: Pd-catalyzed C–C-bond activation of cyclopropenones to synthesize unsaturated esters and amides.
Scheme 75: Ag-catalyzed C–C-bond activation of diphenylcyclopropenone.
Scheme 76: Cu-catalyzed C–C bond activation of diphenylcyclopropenone.
Scheme 77: PPh3-catalyzed C–C-bond activation of diphenylcyclopropenone.
Scheme 78: Catalyst-free C–C-bond activation of diphenylcyclopropenone.
Scheme 79: Cu-catalyzed dioxolane cleavage.
Scheme 80: Multicomponent coupling reactions.
Scheme 81: Pd-catalyzed partial hydrogenation of electrophilic alkynes.
Scheme 82: Nickel and cobalt as earth-abundant transition metals used as catalysts for the partial hydrogenati...
Scheme 83: Metal-free-catalyzed partial hydrogenation of conjugated alkynes.
Scheme 84: Horner–Wadsworth–Emmons reaction between triethyl 2-fluoro-2-phosphonoacetate and aldehydes with ei...
Scheme 85: Preparation of E/Z-cinnamates using thiouronium ylides.
Scheme 86: Transition-metal-catalyzed ylide reactions.
Scheme 87: Redox-driven ylide reactions.
Scheme 88: Noble transition-metal-catalyzed olefination via carbenoid species.
Scheme 89: TrBF4-catalyzed olefination via carbene species.
Scheme 90: Grubbs catalyst (cat 7)/photocatalyst-mediated metathesis reactions.
Scheme 91: Elemental I2-catalyzed carbonyl-olefin metathesis.
Scheme 92: Cu-photocatalyzed E-to-Z isomerization of cinnamic acid derivatives.
Scheme 93: Ni-catalyzed E-to-Z isomerization.
Scheme 94: Dehydration of β-hydroxy esters via an E1cB mechanism to access (E)-cinnamic acid esters.
Scheme 95: Domino ring-opening reaction induced by a base.
Scheme 96: Dehydroamination of α-aminoester derivatives.
Scheme 97: Accessing methyl cinnamate (44) via metal-free deamination or decarboxylation.
Scheme 98: The core–shell magnetic nanosupport-catalyzed condensation reaction.
Scheme 99: Accessing cinnamic acid derivatives from acetic acid esters/amides through α-olefination.
Scheme 100: Accessing cinnamic acid derivatives via acceptorless α,β-dehydrogenation.
Scheme 101: Cu-catalyzed formal [3 + 2] cycloaddition.
Scheme 102: Pd-catalyzed C–C bond formation via 1,4-Pd-shift.
Scheme 103: NHC-catalyzed Rauhut–Currier reactions.
Scheme 104: Heck-type reaction for Cα arylation.
Scheme 105: Cu-catalyzed trifluoromethylation of cinnamamide.
Scheme 106: Ru-catalyzed alkenylation of arenes using directing groups.
Scheme 107: Earth-abundant transition-metal-catalyzed hydroarylation of α,β-alkynyl ester 374.
Scheme 108: Precious transition-metal-catalyzed β-arylation of cinnamic acid amide/ester.
Scheme 109: Pd-catalyzed β-amination of cinnamamide.
Scheme 110: S8-mediated β-amination of methyl cinnamate (44).
Scheme 111: Pd-catalyzed cross-coupling reaction of alkynyl esters with phenylsilanes.
Scheme 112: Pd-catalyzed β-cyanation of alkynyl amide/ester.
Scheme 113: Au-catalyzed β-amination of alkynyl ester 374.
Scheme 114: Metal-free-catalyzed Cβ-functionalizations of alkynyl esters.
Scheme 115: Heck-type reactions.
Scheme 116: Mizoroki–Heck coupling reactions using unconventional functionalized arenes.
Scheme 117: Functional group-directed Mizoroki–Heck coupling reactions.
Scheme 118: Pd nanoparticles-catalyzed Mizoroki–Heck coupling reactions.
Scheme 119: Catellani-type reactions to access methyl cinnamate with multifunctionalized arene.
Scheme 120: Multicomponent coupling reactions.
Scheme 121: Single atom Pt-catalyzed Heck coupling reaction.
Scheme 122: Earth-abundant transition metal-catalyzed Heck coupling reactions.
Scheme 123: Polymer-coated earth-abundant transition metals-catalyzed Heck coupling reactions.
Scheme 124: Earth-abundant transition-metal-based nanoparticles as catalysts for Heck coupling reactions.
Scheme 125: CN- and Si-based directing groups to access o-selective cinnamic acid derivatives.
Scheme 126: Amide-based directing group to access o-selective cinnamic acid derivatives.
Scheme 127: Carbonyl-based directing group to access o-selective cinnamic acid derivatives.
Scheme 128: Stereoselective preparation of atropisomers via o-selective C(sp2)–H functionalization.
Scheme 129: meta-Selective C(sp2)–H functionalization using directing group-tethered arenes.
Scheme 130: para-Selective C(sp2)–H functionalization using directing group-tethered arenes.
Scheme 131: Non-directed C(sp2)–H functionalization via electrooxidative Fujiwara–Moritani reaction.
Scheme 132: Interconversion of functional groups attached to cinnamic acid.
Scheme 133: meta-Selective C(sp2)–H functionalization of cinnamate ester.
Scheme 134: C(sp2)–F arylation using Grignard reagents.
Scheme 135: Truce–Smiles rearrangement of N-aryl metacrylamides.
Scheme 136: Phosphine-catalyzed cyclization of γ-vinyl allenoate with enamino esters.
Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams
- Valentina Giraldi,
- Giandomenico Magagnano,
- Daria Giacomini,
- Pier Giorgio Cozzi and
- Andrea Gualandi
Beilstein J. Org. Chem. 2024, 20, 2461–2468, doi:10.3762/bjoc.20.210
- starting from succinimide (Scheme 3). Through a simple reaction in toluene at 80 °C in the presence of Zn(OAc)2, the hemiaminal derivative 13 underwent substitution with cinnamyl alcohol, resulting in the isolation of 14 with a satisfactory yield. Under optimized reaction conditions, the photocatalytic
Graphical Abstract
Figure 1: A) Photoredox amidocyclization reaction. B) The strongly oxidizing Fukuzumi catalyst (I) used in th...
Figure 2: A) Access of clavam derivatives by intramolecular photoredox reaction of alkenes. B) Clavulanic aci...
Scheme 1: Preparation of alkenyl β-lactam derivatives for the intramolecular photoredox reaction.
Scheme 2: Photoredox-catalyzed intramolecular N-alkylation reactions of various β-lactams. The trans/cis dr w...
Scheme 3: Synthesis of the model substrate 14 and its photoredox-catalyzed intramolecular N-alkylation reacti...
Figure 3: Tentative mechanism for the photo-cyclization reaction.
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.
Cerium-photocatalyzed aerobic oxidation of benzylic alcohols to aldehydes and ketones
- Girish Suresh Yedase,
- Sumit Kumar,
- Jessica Stahl,
- Burkhard König and
- Veera Reddy Yatham
Beilstein J. Org. Chem. 2021, 17, 1727–1732, doi:10.3762/bjoc.17.121
- 1ad and 1ae gave the ketones 2z, 2aa, 2ab, 2ac, 2ad, and 2ae in good yields. However, the primary aliphatic alcohol 3-phenylpropanol (1af) did not provide the desired aldehyde at all, and allylic alcohols such as geraniol (1ag) and cinnamyl alcohol (1ah) afforded the aldehydes 2ag and 2ah in very low
Graphical Abstract
Scheme 1: Photocatalyzed aerobic oxidation of aromatic alcohols.
Scheme 2: Substrate scope. Reaction conditions as given in Table 1 (entry 1). Yields are isolated yields, average of...
Scheme 3: Selective oxidation of 3-bromobenzyl alcohol in the presence of 3-phenylpropanol. Compound 1af was ...
Figure 1: Mechanistic studies. (A): UV–vis spectra of the CeIV(OBn)Cln complex in CH3CN under blue light irra...
Copper catalysis with redox-active ligands
- Agnideep Das,
- Yufeng Ren,
- Cheriehan Hessin and
- Marine Desage-El Murr
Beilstein J. Org. Chem. 2020, 16, 858–870, doi:10.3762/bjoc.16.77
- alcohol to benzaldehyde, the authors also show that reaction with t-BuPhCuO.S.2 (5 mol %) could be efficiently extended to other substrates containing weak C–H bonds and acidic O–H bonds such as diphenylmethanol (PhBzOH), benzoin, and cinnamyl alcohol. However, alcohols with stronger C–H bonds
Graphical Abstract
Scheme 1: Copper complexes with amidophenolate type benzoxazole ligands for alcohol oxidations.
Scheme 2: Copper-catalyzed aerobic oxidation of alcohols and representative substrate scope.
Scheme 3: Introduction of H-bonding network in the ligand coordination sphere.
Scheme 4: Well-defined isatin copper complexes.
Scheme 5: Catalyst control in the biomimetic phenol ortho-oxidation.
Scheme 6: Structural diversity accessible by direct functionalization.
Scheme 7: Copper-catalyzed trifluoromethylation of heteroaromatics with redox-active iminosemiquinone ligands....
Scheme 8: Reversal of helical chirality upon redox stimuli and enantioselective Michael addition with a redox...
Scheme 9: Interaction of guanidine-copper catalyst with oxygen and representative coupling products. a4 mol %...
Scheme 10: Access to 1,2-oxy-aminoarenes by copper-catalyzed phenol–amine coupling.
Scheme 11: Copper-catalyzed aziridination through molecular spin catalysis with redox-active iminosemiquinone ...
Scheme 12: Nitrogen-group and carbon-group transfer in copper-catalyzed aziridination and cyclopropanation thr...
Novel amide-functionalized chloramphenicol base bifunctional organocatalysts for enantioselective alcoholysis of meso-cyclic anhydrides
- Lingjun Xu,
- Shuwen Han,
- Linjie Yan,
- Haifeng Wang,
- Haihui Peng and
- Fener Chen
Beilstein J. Org. Chem. 2018, 14, 309–317, doi:10.3762/bjoc.14.19
- different alcohols (Table 3). Excellent yields with high enantioselectivities were obtained in all cases. The sterically more bulky 2-propanol worked well in this reaction. Allylic alcohol, benzyl alcohol and cinnamyl alcohol were also well compatible in this bifunctional organocatalysis conditions to
Graphical Abstract
Figure 1: Chloramphenicol-base-derived bifunctional organocatalysts.
Figure 2: Design of new chloramphenicol base amide organocatalysts.
Scheme 1: Synthesis of bifunctional amide catalysts 7a–q.
Scheme 2: Asymmetric synthesis of (S)-GABOB (13).
Mechanically induced oxidation of alcohols to aldehydes and ketones in ambient air: Revisiting TEMPO-assisted oxidations
- Andrea Porcheddu,
- Evelina Colacino,
- Giancarlo Cravotto,
- Francesco Delogu and
- Lidia De Luca
Beilstein J. Org. Chem. 2017, 13, 2049–2055, doi:10.3762/bjoc.13.202
- oxidative procedure was also applied to allylic alcohol derivatives. Cinnamyl alcohol (1m) was transformed into the corresponding α,β-unsaturated aldehyde in an excellent yield (96%) and with the stereochemical retention of the double bond. Encouraged by these promising results, we attempted to oxidise
Graphical Abstract
Scheme 1: TEMPO-catalysed aerobic oxidative procedures of alcohols. a) Anelli–Montanari protocol: NaOCl (1.25...
Scheme 2: TEMPO-assisted oxidation of 4-nitrobenzylic alcohol under mechanical activation conditions [65].
Scheme 3: Scope of primary alcohols in oxidation under ambient air.
Scheme 4: Scope of secondary alcohols in oxidation under ambient air.
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
- and remarkable catalyst stability over a period of 24 h (Table 2, entries 17, 18). The heterogeneous hydrogenation of the parent alkyne substrate 3-phenyl-2-propyn-1-ol (12) is of interest because the corresponding alkene, the cinnamyl alcohol (12a + 12b), is used in the formulation of perfumes and
Graphical Abstract
Scheme 1: Common reaction pathways for alkyne hydrogenation reactions.
Figure 1: Schematic representation of most common reactor types for batch and continuous-flow partial hydroge...
Figure 2: Schematic representation of flow regimes in microchannels; (a) bubbly flow, (b) slug/Taylor or segm...
Figure 3: Sketch of typical continuous flow apparatus for liquid-phase catalytic alkynes hydrogenation reacti...
Scheme 2: Hydrogenation reactions of terminal alkynes with potential products and labelling scheme.
Figure 4: Structure of Pd@mpg-C3N4 (a), Pd(HHDMA)@C (b), Pd(Pb)@CaCO3 (c) and Pd@Al2O3 (d) catalysts. The str...
Figure 5: Sketch of composition (left) and optical image of Pd@MonoBor monolithic reactor (right). Adapted wi...
Figure 6: X-ray tomography 3D-reconstruction image of MonoBor [133]. Unpublished image from the authors.
Figure 7: Representative TEM image of titanate nanotubes with immobilized PdNP (arrows). Adapted with permiss...
Figure 8: Conversion and selectivity vs. time-on-stream for the continuous-flow hydrogenation of 6 over Pd@Mo...
Figure 9: Continuous-flow hydrogenation of 3, 6 and 7 over different catalytic reactor systems. Data from ref...
Scheme 3: Hydrogenation reactions of internal alkynes with potential products and labelling scheme.
Figure 10: Continuous-flow hydrogenation of 11 over Pd@MonoBor catalyst. a) Conversion and selectivity as a fu...
Figure 11: Conversion and selectivity vs time-on-stream for the continuous-flow hydrogenation of 11 over Pd@Mo...
Figure 12: Continuous-flow hydrogenation reaction of 11 over packed-bed catalysts. Adapted with permission fro...
Figure 13: Images of the bimodal TiO2 monolith with well-defined macroporosity: (a, b) optical; (c) X-ray tomo...
Figure 14: Selectivity of the continuous-flow partial hydrogenation reaction of 3 and 4 over packed-bed Pd cat...
Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid
- Federica Santoro,
- Matteo Mariani,
- Federica Zaccheria,
- Rinaldo Psaro and
- Nicoletta Ravasio
Beilstein J. Org. Chem. 2016, 12, 2627–2635, doi:10.3762/bjoc.12.259
- reaction of optically active (R)-1-phenylethanol gave a completely racemic compound (Scheme 1). Unfortunately allylic alcohols gave unreproducible results. However, in the case of cinnamyl alcohol (1i) we could obtain a fairly good selectivity to the product of the thiol–ene reaction 3p (Scheme 2). The
- benzylmercaptan (2a) in the presence of SiAl 0.6. Reaction of cinnamyl alcohol 1i and benzylmercaptan (2a). Thioethers synthesis in solvent with different catalystsa. Synthesis of thioethers from different alcohols and thiols promoted by SiAl 0.6 without solventa. Supporting Information Supporting Information
Graphical Abstract
Figure 1: Overview of the structures of the alcohols 1a–i used in the present work.
Figure 2: Structures of thiols 2a–f used in the present work.
Figure 3: Structures of thioethers 3a–p synthesized.
Figure 4: Product distribution during reaction of 5b and 2a over a solid acid catalyst.
Figure 5: Product distribution during reaction of 1c and 2e.
Scheme 1: Racemization of (R)-1-phenylethanol during the reaction with benzylmercaptan (2a) in the presence o...
Scheme 2: Reaction of cinnamyl alcohol 1i and benzylmercaptan (2a).
Figure 6: Recyclability test of SiAl 0.6 catalyst in the reaction of 1a and 2a.
A novel and practical asymmetric synthesis of dapoxetine hydrochloride
- Yijun Zhu,
- Zhenren Liu,
- Hongyan Li,
- Deyong Ye and
- Weicheng Zhou
Beilstein J. Org. Chem. 2015, 11, 2641–2645, doi:10.3762/bjoc.11.283
- encompass asymmetric dihydroxylation of trans-methyl cinnamate or cinnamyl alcohol [6], chiral azetidin-2,3-dione [7], asymmetric C–H amination reactions of a prochiral sulfamate [8], oxazaborolidine reduction of 3-chloropropiophenone or ketone [9], and an imidazolidin-2-one chiral auxiliary mediated
Graphical Abstract
Figure 1: Dapoxetine hydrochloride (1).
Scheme 1: Asymmetric synthesis of 1.
Scheme 2: Reduction of sulfinylimine 4.
Phosphinate-containing heterocycles: A mini-review
- Olivier Berger and
- Jean-Luc Montchamp
Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67
- 2 equivalents of cinnamyl alcohol 44 in the presence of 2 mol % of Pd/Xanthpos followed by an esterification using benzyl bromide. Ozonolysis, and reductive amination using excess benzylamine in the presence of sodium cyanoborohydride completed the synthesis. Phosphorines Two phosphorines 47a,b were
Graphical Abstract
Scheme 1: McCormack synthesis.
Scheme 2: Ring-closing metathesis.
Scheme 3: Phospha-Dieckmann condensation.
Scheme 4: Palladium-catalyzed oxidative arylation.
Scheme 5: Tandem cross-coupling/Dieckmann condensation.
Scheme 6: Rhodium-catalyzed double [2 + 2 + 2] cycloaddition.
Scheme 7: Silver oxide-mediated alkyne–arene annulation.
Scheme 8: Silver acetate-mediated alkyne–arene annulation.
Scheme 9: Cyclization through phosphinylation/alkylation of malonate anion.
Scheme 10: Tandem hydrophosphinylation/Michael/Michael reaction of allenyl-H-phosphinates.
Scheme 11: 5-Membered “cyclo-PALA” via intramolecular Mitsunobu reaction.
Scheme 12: 6-Membered “cyclo-PALA” via intramolecular Mitsunobu reaction.
Scheme 13: Intramolecular Kabachnik–Fields reaction.
Scheme 14: Tandem Kabachnik–Fields/alkylation reaction.
Scheme 15: Tandem Kabacknik–Fields/C–N cross-coupling reaction.
Scheme 16: Tandem Kabacknik–Fields/C-P cross-coupling reaction.
Scheme 17: Heterocyclization via amide formation.
Scheme 18: Cyclization via reductive amination.
Scheme 19: H-Phosphinate alkylation.
Scheme 20: Cyclization through intramolecular Michael addition.
Scheme 21: Double Arbuzov reaction of bis(trimethylsiloxy)phosphine.
Scheme 22: Diastereoselective ring-closing metathesis.
Scheme 23: 2-Ketophosphonate/benzene annulation.
Scheme 24: Tandem Kabachnik–Fields/transesterification reaction.
Scheme 25: Tandem Kabachnik–Fields/transesterification reaction with oxazolidine.
A new intermediate in the Prins reaction
- Shinichi Yamabe,
- Takeshi Fukuda and
- Shoko Yamazaki
Beilstein J. Org. Chem. 2013, 9, 476–485, doi:10.3762/bjoc.9.51
- TS1(Ph). A noticeable difference is found in the contrast of the stability order, ene-ol(Ph) > ether(Ph) versus ene-ol(Me) < ether(Me). The 3-phenyl-2-propenol (cinnamyl alcohol) is an allylic alcohol with the π conjugation of the phenyl ring and is thought to be the source of the stability of ene-ol
Graphical Abstract
Scheme 1: A general scheme of the Prins reaction.
Scheme 2: An example of the Prins reaction [4]. The product yields (%) are based on formaldehyde.
Scheme 3: An equilibrium in the hydrolysis of the product, 1,3-dioxane.
Scheme 4: Formation of the acetate of an allylic alcohol by Prins reaction [5].
Scheme 5: A reaction mechanism involving the carbonium-ion intermediate X.
Scheme 6: A reaction model composed of RHC=CH2, (H2C=O)2 and H3O+(H2O)13 to obtain the path of step 2 (Scheme 5). H3O+...
Figure 1: Geometries of the precursor and the transition states (TSs) of the Prins reaction of propene with (...
Figure 2: Energy changes (in kcal/mol) of the propene Prins reaction calculated by B3LYP/6-311+G(d,p) SCRF=(P...
Figure 3: Geometries of the transition states (TSs) of the Prins reaction of styrene + (formaldehyde)2 + H3O+...
Figure 4: Energy changes (in kcal/mol) of the styrene Prins reaction calculated by B3LYP/6-311+G(d,p) SCRF = ...
Figure 5: TS1(Ph) geometries of n = 20 and n = 30 in the reacting system of styrene + H3O+(H2O)n + (H2C=O)2 c...
Scheme 7: Summary of the present calculated results. The ether in the box is the new intermediate found in th...
Inter- and intramolecular enantioselective carbolithiation reactions
- Asier Gómez-SanJuan,
- Nuria Sotomayor and
- Esther Lete
Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36
- -disubstituted vinylcyclopropanes 8 in moderate to good enantiomeric excesses (Scheme 2b) [11]. More recently, enantioselective carbolithiation of cinnamyl alcohol has been reinvestigated by using (+)-sparteine surrogates, such as diamine L2 [12]. The best results are obtained by the treatment of cinnamyl
- fully developed. On the other hand, the high reactivity of the organolithiums requires the use of stoichiometric amounts of the chiral ligand. Intermolecular carbolithiation. Carbolithiation of cinnamyl and dienyl derivatives. Carbolithiation of cinnamyl alcohol. Carbolithiation of styrene derivatives
- alcohol (9) with the complex of butyllithium/diamine L2 in cumene at 0 °C, obtaining alcohol (R)-11 in 71% yield with 71% ee (Scheme 3). This is essentially opposite to the enantioselectivity obtained previously with (−)-sparteine L1 (82% yield, 83% ee in favor of (S)-11) [10]. Substituted styrene
Graphical Abstract
Scheme 1: Intermolecular carbolithiation.
Scheme 2: Carbolithiation of cinnamyl and dienyl derivatives.
Scheme 3: Carbolithiation of cinnamyl alcohol.
Scheme 4: Carbolithiation of styrene derivatives.
Scheme 5: Carbolithiation of α-aryl O-alkenyl carbamates.
Scheme 6: Carbolithiation-rearrangement of N-alkenyl-N-arylureas.
Scheme 7: Carbolithiation of N,N-dimethylaminofulvene.
Scheme 8: Carbolithiation of enynes.
Scheme 9: Intramolecular carbolithiation.
Scheme 10: Carbolithiation of 5-alkenylcarbamates.
Scheme 11: Carbolithiation of cinnamylpiperidines.
Scheme 12: Carbolithiation of alkenylpyrrolidines.
Scheme 13: Enantioselective carbolithiation of N-allyl-2-bromoanilines.
Scheme 14: Effect of the ligand in the carbolithiation reaction.
Scheme 15: Effect of the alkene substitution in the carbolithiation reaction.
Scheme 16: Effect of the ring substitution in the carbolithiation reaction.
Scheme 17: Enantioselective carbolithiation of allyl aryl ethers.
Scheme 18: Formation of six-membered rings: pyrroloisoquinolines.
Scheme 19: Formation of six-membered rings: tetrahydroquinolines.
A surprising new route to 4-nitro-3-phenylisoxazole
- Henning Hopf,
- Aboul-fetouh E. Mourad and
- Peter G. Jones
Beilstein J. Org. Chem. 2010, 6, No. 68, doi:10.3762/bjoc.6.68
- , Technische Universität Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany 10.3762/bjoc.6.68 Abstract A one-pot synthesis of 4-nitro-3-phenylisoxazole has been carried out by treatment of cinnamyl alcohol dissolved in acetic acid with sodium nitrite; in addition, 4-phenyl-3-furoxanmethanol was
- obtained in 40% yield. Keywords: cinnamyl alcohol; furoxan derivatives; isoxazole derivatives; X-ray diffraction; Introduction The isoxazole ring system, which can be easily obtained by [3 + 2] cycloaddition of nitric oxides to alkynes, is of interest since it forms a part of various biodynamic agents
- phenylfuroxans 2 and 3 [10]. According to the original report, 4-phenyl-3-furoxanmethanol (2) was obtained as the sole product in 40% yield, by treatment of cinnamyl alcohol (1) dissolved in acetic acid with concentrated aqueous sodium nitrite at 70 °C (Scheme 1). Results and Discussion Application of this
Graphical Abstract
Scheme 1: Preparation of 2 and 4 by treatment of cinnamyl alcohol (1).
Figure 1: The crystal structure of compound 4. Ellipsoids correspond to 50% probability levels.
Figure 2: Packing diagram of compound 4 viewed perpendicular to (101). Hydrogen bonds are indicated by thick ...
Scheme 2: Suggested mechanism for the formation of 4.
A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis
- Magnus Rueping and
- Boris J. Nachtsheim
Beilstein J. Org. Chem. 2010, 6, No. 6, doi:10.3762/bjoc.6.6
- . Other allylating reagents, such as β-methyl-, α,α-, and γ,γ-dimethylallyl alcohols or cinnamyl alcohol could also be used in this reaction. Additionally, high selectivity towards the linear allylated indoles was observed. Surprisingly, N-allylation did not occur. With L-tryptophan methyl ester (73) as
Graphical Abstract
Scheme 1: AlCl3-mediated reaction between amyl chloride and benzene as developed by Friedel and Crafts.
Figure 1: Most often used metal salts for catalytic FC alkylations and hydroarylations of arenes.
Figure 2: 1,1-diarylalkanes with biological activity.
Scheme 2: Alkylating reagents and side products produced.
Scheme 3: Initially reported TeCl4-mediated FC alkylation of 1-penylethanol with toluene.
Scheme 4: Sc(OTf)3-catalyzed FC benzylation of arenes.
Scheme 5: Reductive FC alkylation of arenes with arenecarbaldehydes.
Scheme 6: Iron(III)-catalyzed FC benzylation of arenes and heteroarenes.
Scheme 7: A gold(III)-catalyzed route to beclobrate.
Scheme 8: Catalytic FC-type alkylations of 1,3-dicarbonyl compounds.
Scheme 9: Iron(III)-catalyzed synthesis of phenprocoumon.
Scheme 10: Bi(OTf)3-catalyzed FC alkylation of benzyl alcohols developed by Rueping et al.
Scheme 11: (A) Bi(OTf)3-catalyzed intramolecular FC alkylation as an efficient route to substituted fulvenes. ...
Scheme 12: FC-type glycosylation of 1,2-dimethylindole and trimethoxybenzene.
Scheme 13: FC alkylation with highly reactive ferrocenyl- and benzyl alcohols. The reaction proceeds even with...
Scheme 14: Reductive FC alkylation of arenes with benzaldehyde and acetophenone catalyzed by the Ir-carbene co...
Scheme 15: Formal synthesis of 1,1-diarylalkanes from benzyl alcohols and styrenes.
Scheme 16: (A) Mo-catalyzed hydroarylation of styrenes and cyclohexenes. (B) Hydroalkylation–cyclization casca...
Scheme 17: Bi(III)-catalyzed hydroarylation of styrenes with arenes and heteroarenes.
Scheme 18: BiCl3-catalyzed ene/FC alkylation reaction cascade – A fast access to highly arylated dihydroindene...
Scheme 19: Au(I)/Ag(I)-catalyzed hydroarylation of indoles with styrenes, aliphatic and cyclic alkenes.
Scheme 20: First transition-metal-catalyzed ortho-hydroarylation developed by Beller et al.
Scheme 21: (A) Ti(IV)-mediated rearrangement of an N-benzylated aniline to the corresponding ortho-alkylated a...
Scheme 22: Dibenzylation of aniline gives potentially useful amine-based ligands in a one-step procedure.
Scheme 23: FC-type alkylations with allyl alcohols as alkylating reagents – linear vs. branched product format...
Scheme 24: (A) First catalytic FC allylation and cinnamylation using allyl alcohols and its derivatives. (B) E...
Scheme 25: FC allylation/cyclization reaction yielding substituted chromanes.
Scheme 26: Synthesis of (all-rac)-α-tocopherol utilizing Lewis- and strong Brønsted-acids.
Scheme 27: Au(III)-catalyzed cinnamylation of arenes.
Scheme 28: “Exhaustive” allylation of benzene-1,3,5-triol.
Scheme 29: Palladium-catalyzed allylation of indole.
Scheme 30: Pd-catalyzed synthesis of pyrroloindoles from L-tryptophane.
Scheme 31: Ru(IV)-catalyzed allylation of indole and pyrroles with unique regioselectivity.
Scheme 32: Silver(I)-catalyzed intramolecular FC-type allylation of arenes and heteroarenes.
Scheme 33: FC-type alkylations of arenes using propargyl alcohols.
Scheme 34: (A) Propargylation of arenes with stoichiometric amounts of the Ru-allenylidene complex 86. (B) Fir...
Scheme 35: Diruthenium-catalyzed formation of chromenes and 1H-naphtho[2,1-b]pyrans.
Scheme 36: Rhenium(V)-catalyzed FC propargylations as a first step in the total synthesis of podophyllotoxin, ...
Scheme 37: Scandium-catalyzed arylation of 3-sulfanyl- and 3-selanylpropargyl alcohols.
Scheme 38: Synthesis of 1,3-diarylpropynes via direct coupling of propargyl trichloracetimidates and arenes.
Scheme 39: Diastereoselective substitutions of benzyl alcohols.
Scheme 40: (A) First diastereoselective FC alkylations developed by Bach et al. (B) anti-Selective FC alkylati...
Scheme 41: Diastereoselective AuCl3-catalyzed FC alkylation.
Scheme 42: Bi(OTf)3-catalyzed alkylation of α-chiral benzyl acetates with silyl enol ethers.
Scheme 43: Bi(OTf)3-catalyzed diastereoselective substitution of propargyl acetates.
Scheme 44: Nucelophilic substitution of enantioenriched ferrocenyl alcohols.
Scheme 45: First catalytic enantioselective propargylation of arenes.
A short stereoselective synthesis of (+)-(6R,2′S)-cryptocaryalactone via ring- closing metathesis
- Palakodety Radha Krishna,
- Krishnarao Lopinti and
- K. L. N. Reddy
Beilstein J. Org. Chem. 2009, 5, No. 14, doi:10.3762/bjoc.5.14
- THF at 0 °C to give cinnamyl alcohol derivative 14 (87%, Scheme 3). Alcohol 14 was protected as its acetate under conventional reaction conditions. The PMB (p-methoxybenzyl protecting group) in compound 15 was selectively removed with DDQ in CH2Cl2/H2O (19:1) to afford homoallylic alcohol 16 (89
Graphical Abstract
Figure 1: Some natural products containing styryl lactones.
Figure 2: Retrosynthetic approach.
Scheme 1: Synthesis of chiral propargyl secondary hydroxyl group.
Scheme 2: Determination of the stereochemistry of the 1,3-anti diols.
Scheme 3: Synthesis of cryptocaryalactone by RCM.
