A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions
- Munmun Ghosh,
- Valmik S. Shinde and
- Magnus Rueping
Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264
Graphical Abstract
Figure 1: General classification of asymmetric electroorganic reactions.
Scheme 1: Asymmetric reduction of 4-acetylpyridine using a modified graphite cathode.
Scheme 2: Asymmetric hydrogenation of ketones using Raney nickel powder electrodes modified with optically ac...
Scheme 3: Asymmetric reduction of prochiral activated olefins with a poly-ʟ-valine-coated graphite cathode.
Scheme 4: Asymmetric reduction of prochiral carbonyl compounds, oximes and gem-dibromides on a poly-ʟ-valine-...
Scheme 5: Asymmetric hydrogenation of prochiral ketones with poly[RuIII(L)2Cl2]+-modified carbon felt cathode...
Scheme 6: Asymmetric hydrogenation of α-keto esters using chiral polypyrrole film-coated cathode incorporated...
Scheme 7: Quinidine and cinchonidine alkaloid-induced asymmetric electroreduction of acetophenone.
Scheme 8: Asymmetric electroreduction of 4- and 2-acetylpyridines at a mercury cathode in the presence of a c...
Scheme 9: Enantioselective reduction of 4-methylcoumarin in the presence of catalytic yohimbine.
Scheme 10: Cinchonine-induced asymmetric electrocarboxylation of 4-methylpropiophenone.
Scheme 11: Enantioselective hydrogenation of methyl benzoylformate using an alkaloid entrapped silver cathode.
Scheme 12: Alkaloid-induced enantioselective hydrogenation using a Cu nanoparticle cathode.
Scheme 13: Alkaloid-induced enantioselective hydrogenation of aromatic ketones using a bimetallic Pt@Cu cathod...
Scheme 14: Enantioselective reduction of ketones at mercury cathode using N,N'-dimethylquininium tetrafluorobo...
Scheme 15: Asymmetric synthesis of an amino acid using an electrode modified with amino acid oxidase and elect...
Scheme 16: Asymmetric oxidation of p-tolyl methyl sulfide using chemically modified graphite anode.
Scheme 17: Asymmetric oxidation of unsymmetric sulfides using poly(amino acid)-coated electrodes.
Scheme 18: Enantioselective, electocatalytic oxidative coupling on TEMPO-modified graphite felt electrode in t...
Scheme 19: Asymmetric electrocatalytic oxidation of racemic alcohols on a TEMPO-modified graphite felt electro...
Scheme 20: Asymmetric electrocatalytic lactonization of diols on TEMPO-modified graphite felt electrodes.
Scheme 21: Asymmetric electrochemical pinacolization in a chiral solvent.
Scheme 22: Asymmetric electroreduction using a chiral supporting electrolyte.
Scheme 23: Asymmetric anodic oxidation of enol acetates using chiral supporting electrolytes.
Scheme 24: Kinetic resolution of primary amines using a chiral N-oxyl radical mediator.
Scheme 25: Chiral N-oxyl-radical-mediated kinetic resolution of secondary alcohols via electrochemical oxidati...
Scheme 26: Chiral iodoarene-mediated asymmetric electrochemical lactonization.
Scheme 27: Os-catalyzed electrochemical asymmetric dihydroxylation of olefins using the Sharpless ligand and i...
Scheme 28: Asymmetric electrochemical epoxidation of olefins catalyzed by a chiral Mn-salen complex.
Scheme 29: Asymmetric electrooxidation of 1,2-diols, and amino alcohols using a chiral copper catalyst.
Scheme 30: Mechanism of asymmetric electrooxidation of 1,2-diols, and amino alcohols using a chiral copper cat...
Scheme 31: Enantioselective electrocarboxylation catalyzed by an electrogenerated chiral [CoI(salen)]− complex....
Scheme 32: Asymmetric oxidative cross coupling of 2-acylimidazoles with silyl enol ethers.
Scheme 33: Ni-catalyzed asymmetric electroreductive cleavage of allylic β-keto ester 89.
Scheme 34: Asymmetric alkylation using a combination of electrosynthesis and a chiral Ni catalyst.
Scheme 35: Mechanism of asymmetric alkylation using a combination of electrosynthesis and a chiral Ni catalyst....
Scheme 36: Asymmetric epoxidation by electrogenerated percarbonate and persulfate ions in the presence of chir...
Scheme 37: α-Oxyamination of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 38: The α-alkylation of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 39: Mechanism of α-alkylation of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 40: Electrochemical chiral secondary amine-catalyzed intermolecular α-arylation of aldehydes.
Scheme 41: Mechanism of electrochemical chiral secondary amine-catalyzed intermolecular α-arylation of aldehyd...
Scheme 42: Asymmetric cross-dehydrogenative coupling of tertiary amines with simple ketones via an electrochem...
Scheme 43: Electroenzymatic asymmetric reduction using enoate reductase.
Scheme 44: Assymetric reduction using alcohol dehydrogenase as the electrocatalyst.
Scheme 45: Asymmetric electroreduction catalyzed by thermophilic NAD-dependent alcohol dehydrogenase.
Scheme 46: Asymmetric epoxidation of styrene by electrochemical regeneration of flavin-dependent monooxygenase....
Scheme 47: Asymmetric electroreduction using a chloroperoxidase catalyst.
Scheme 48: Asymmetric electrochemical transformation mediated by hydrophobic vitamin B12.
Scheme 49: Diastereoselective cathodic reduction of phenylglyoxalic acids substituted with amines as chiral au...
Scheme 50: Ni-catalyzed asymmetric electroreductive cross coupling of aryl halides with α-chloropropanoic acid...
Scheme 51: Electrochemical Mannich addition of silyloxyfuran to in situ-generated N-acyliminium ions.
Scheme 52: Stereoselective electroreductive homodimerization of cinnamates attached to a camphor-derived chira...
Scheme 53: Diastereoselective electrochemical carboxylation of chiral α-bromocarboxylic acid derivatives.
Scheme 54: Electrocatalytic stereoselective conjugate addition of chiral β-dicarbonyl compounds to methyl viny...
Scheme 55: Stereoselective electrochemical carboxylation of chiral cinnamic acid derivatives under a CO2 atmos...
Scheme 56: Electrochemical diastereoselective α-alkylation of pyrrolidines attached with phosphorus-derived ch...
Scheme 57: Electrogenerated cyanomethyl anion-induced synthesis of chiral cis-β-lactams from amides bearing ch...
Scheme 58: Diastereoselective anodic oxidation followed by intramolecular cyclization of ω-hydroxyl amides bea...
Scheme 59: Electrochemical deprotonation of Ni(II) glycinate containing (S)-BPB as a chiral auxiliary: diaster...
Scheme 60: Enantioselective electroreductive coupling of diaryl ketones with α,β-unsaturated carbonyl compound...
Scheme 61: Asymmetric total synthesis of ropivacaine and its analogues using a electroorganic reaction as a ke...
Scheme 62: Asymmetric total synthesis of (−)-crispine A and its natural enantiomer via anodic cyanation of tet...
Scheme 63: Asymmetric oxidative electrodimerization of cinnamic acid derivatives as key step for the synthesis...
Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal
- Carlos Vila,
- Jonathan Lau and
- Magnus Rueping
Beilstein J. Org. Chem. 2014, 10, 1233–1238, doi:10.3762/bjoc.10.122
Graphical Abstract
Figure 1: Representative examples of lamellarin alkaloids.
Scheme 1: Photocatalytic metal free construction of pyrrolo[2,1-a]isoquinolines.
Scheme 2: Evaluation of the substrate scope.
Scheme 3: Evaluation of the substrate scope with activated alkynes.
A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines
- Erli Sugiono and
- Magnus Rueping
Beilstein J. Org. Chem. 2013, 9, 2457–2462, doi:10.3762/bjoc.9.284
Graphical Abstract
Scheme 1: Photocyclization–reduction of 2-aminochalcone.
Scheme 2: Experimental setup of continuous-flow photocyclization–reduction cascade.
Continuous flow photocyclization of stilbenes – scalable synthesis of functionalized phenanthrenes and helicenes
- Quentin Lefebvre,
- Marc Jentsch and
- Magnus Rueping
Beilstein J. Org. Chem. 2013, 9, 1883–1890, doi:10.3762/bjoc.9.221
Graphical Abstract
Scheme 1: Photocyclization of stilbene to phenanthrene.
Figure 1: Flow-reactor setup used in the optimization study.
Scheme 2: Photo-flow synthesis of [5]- and [6]helicenes. aFor experimental details see Supporting Information File 1. bReaction conditions...
Scheme 3: Scale up synthesis of the [5]helicene derivative 2o.
Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene
- Magnus Rueping and
- Sadiya Raja
Beilstein J. Org. Chem. 2012, 8, 1819–1824, doi:10.3762/bjoc.8.208
Graphical Abstract
Scheme 1: Brønsted acid catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene.
Continuous-flow catalytic asymmetric hydrogenations: Reaction optimization using FTIR inline analysis
- Magnus Rueping,
- Teerawut Bootwicha and
- Erli Sugiono
Beilstein J. Org. Chem. 2012, 8, 300–307, doi:10.3762/bjoc.8.32
Graphical Abstract
Scheme 1: Experimental setup for the asymmetric transfer hydrogenation.
Scheme 2: Asymmetric hydrogenation of benzoxazines.
Figure 1: In situ ReactIR monitoring: (a) Trend curve of product formation at different temperatures. (b) Rea...
Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst
- Magnus Rueping,
- Teerawut Bootwicha,
- Hannah Baars and
- Erli Sugiono
Beilstein J. Org. Chem. 2011, 7, 1680–1687, doi:10.3762/bjoc.7.198
Graphical Abstract
Scheme 1: The schematic arrangement of the continuous-flow system.
Scheme 2: Preparation of chalcone 3b on larger scale.
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
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.
