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Search for "Lewis-acid catalysis" in Full Text gives 38 result(s) in Beilstein Journal of Organic Chemistry.
Silver and gold-catalyzed multicomponent reactions
- Giorgio Abbiati and
- Elisabetta Rossi
Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46
- -catalyzed process described in Scheme 31 takes advantage of the usual formation of 43 which undergoes a [3 + 3]-cycloaddition reaction with cyclopropanes 59 under nickel perchlorate catalysis. Cycloaddition reactions of activated cyclopropanes with nitrones under Lewis acid catalysis have been previously
Graphical Abstract
Scheme 1: General reaction mechanism for Ag(I)-catalyzed A3-coupling reactions.
Scheme 2: A3-coupling reaction catalyzed by polystyrene-supported NHC–silver halides.
Figure 1: Various NHC–Ag(I) complexes used as catalysts for A3-coupling.
Scheme 3: Proposed reaction mechanism for NHC–AgCl catalyzed A3-coupling reactions.
Scheme 4: Liu’s synthesis of pyrrole-2-carboxaldehydes 4.
Scheme 5: Proposed reaction mechanism for Liu’s synthesis of pyrrole-2-carboxaldehydes 4.
Scheme 6: Gold-catalyzed synthesis of propargylamines 1.
Scheme 7: A3-coupling catalyzed by phosphinamidic Au(III) metallacycle 6.
Scheme 8: Gold-catalyzed KA2-coupling.
Scheme 9: A3-coupling applied to aldehyde-containing oligosaccharides 8.
Scheme 10: A3-MCR for the preparation of propargylamine-substituted indoles 9.
Scheme 11: A3-coupling interceded synthesis of furans 12.
Scheme 12: A3/KA2-coupling mediated synthesis of functionalized dihydropyrazoles 13 and polycyclic dihydropyra...
Scheme 13: Au(I)-catalyzed entry to cyclic carbamimidates 17 via an A3-coupling-type approach.
Scheme 14: Proposed reaction mechanism for the Au(I)-catalyzed synthesis of cyclic carbamimidates 17.
Figure 2: Chiral trans-1-diphenylphosphino-2-aminocyclohexane–Au(I) complex 20.
Scheme 15: A3-coupling-type synthesis of oxazoles 21 catalyzed by Au(III)–salen complex.
Scheme 16: Proposed reaction mechanism for the synthesis of oxazoles 21.
Scheme 17: Synthesis of propargyl ethyl ethers 24 by an A3-coupling-type reaction.
Scheme 18: General mechanism of Ag(I)-catalyzed MCRs of 2-alkynylbenzaldehydes, amines and nucleophiles.
Scheme 19: General synthetic pathway to 1,3-disubstituted-1,2-dihydroisoquinolines.
Scheme 20: Synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 29.
Scheme 21: Synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 35 and 36.
Scheme 22: Rh(II)/Ag(I) co-catalyzed synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 40.
Scheme 23: General synthetic pathway to 2-amino-1,2-dihydroquinolines.
Scheme 24: Synthesis of 2-amino-1,2-dihydroquinolines 47.
Scheme 25: Synthesis of tricyclic H-pyrazolo[5,1-a]isoquinoline 48.
Scheme 26: Synthesis of tricyclic H-pyrazolo[5,1-a]isoquinolines 48.
Scheme 27: Cu(II)/Ag(I) catalyzed synthesis of H-pyrazolo[5,1-a]isoquinolines 48.
Scheme 28: Synthesis of 2-aminopyrazolo[5,1-a]isoquinolines 53.
Scheme 29: Synthesis of 1-(isoquinolin-1-yl)guanidines 55.
Scheme 30: Ag(I)/Cu(I) catalyzed synthesis of 2-amino-H-pyrazolo[5,1-a]isoquinolines 58.
Scheme 31: Ag(I)/Ni(II) co-catalyzed synthesis of 3,4-dihydro-1H-pyridazino[6,1-a]isoquinoline-1,1-dicarboxyla...
Scheme 32: Ag(I) promoted activation of the α-carbon atom of the isocyanide group.
Scheme 33: Synthesis of dihydroimidazoles 65.
Scheme 34: Synthesis of oxazoles 68.
Scheme 35: Stereoselective synthesis of chiral butenolides 71.
Scheme 36: Proposed reaction mechanism for the synthesis of butenolides 71.
Scheme 37: Stereoselective three-component approach to pirrolidines 77 by means of a chiral auxiliary.
Scheme 38: Stereoselective three-component approach to pyrrolidines 81 and 82 by means of a chiral catalyst.
Scheme 39: Synthesis of substituted five-membered carbocyles 86.
Scheme 40: Synthesis of regioisomeric arylnaphthalene lactones.
Scheme 41: Enantioselective synthesis of spiroacetals 96 by Fañanás and Rodríguez [105].
Scheme 42: Enantioselective synthesis of spiroacetals 101 by Gong [106].
Scheme 43: Synthesis of polyfunctionalized fused bicyclic ketals 103 and bridged tricyclic ketals 104.
Scheme 44: Proposed reaction mechanism for the synthesis of ketals 103 and 104.
Scheme 45: Synthesis of β-alkoxyketones 108.
Scheme 46: Synthesis of N-methyl-1,4-dihydropyridines 112.
Scheme 47: Synthesis of tetrahydrocarbazoles 115–117.
Scheme 48: Plausible reaction mechanism for the synthesis of tetrahydrocarbazoles 115–117.
Scheme 49: Carboamination, carboalkoxylation and carbolactonization of terminal alkenes.
Scheme 50: Oxyarylation of alkenes with arylboronic acids and Selectfluor as reoxidant.
Scheme 51: Proposed reaction mechanism for oxyarylation of alkenes.
Scheme 52: Oxyarylation of alkenes with arylsilanes and Selectfluor as reoxidant.
Scheme 53: Oxyarylation of alkenes with arylsilanes and IBA as reoxidant.
Studies on the interaction of isocyanides with imines: reaction scope and mechanistic variations
- Ouldouz Ghashghaei,
- Consiglia Annamaria Manna,
- Esther Vicente-García,
- Marc Revés and
- Rodolfo Lavilla
Beilstein J. Org. Chem. 2014, 10, 12–17, doi:10.3762/bjoc.10.3
- Barcelona, Spain 10.3762/bjoc.10.3 Abstract The interaction of imines with isocyanides has been studied. The main product results from a sequential process involving the attack of two units of isocyanide, under Lewis acid catalysis, upon the carbon–nitrogen double bond of the imine to form the 4-membered
Graphical Abstract
Scheme 1: Azetidine formation from the interaction of imines with isocyanides.
Scheme 2: Reaction conditions.
Figure 1: X-ray diffraction analysis of azetidine 3a.
Scheme 3: Stepwise mechanism for the formation of azetidine 3a.
Scheme 4: Manifold reaction mechanism.
Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor
- Rajesh Munirathinam,
- Roberto Ricciardi,
- Richard J. M. Egberink,
- Jurriaan Huskens,
- Michael Holtkamp,
- Herbert Wormeester,
- Uwe Karst and
- Willem Verboom
Beilstein J. Org. Chem. 2013, 9, 1698–1704, doi:10.3762/bjoc.9.194
- model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3. Keywords: dehydration of oximes; flow chemistry; gallium; microreactors; Lewis acid catalysis
- easy fabrication of the catalytic device by filling the channels with functional catalytic particles, however, heat transfer limitations and pressure drop developing along the microchannel are serious drawbacks [7]. The literature contains numerous examples of Lewis acid catalysis [8][9][10][11
- ]. However, only a limited number of papers are known dealing with heterogeneous Lewis acid catalysis, where a Lewis acid is tethered onto a solid surface like silica or gold [12][13]. Furthermore, to the best of our knowledge, there are no examples of the immobilization of a Lewis acid to a microreactor
Graphical Abstract
Scheme 1: Gallium-catalyzed dehydration of cinnamaldehyde oxime (1).
Scheme 2: General scheme for anchoring of initiator, ATRP of styrene sulfonate, activation, and reaction with...
Figure 1: Gallium-catalyzed formation of nitrile 2 at 90 °C and 5 atm pressure.
Figure 2: Arrhenius plot for the dehydration of cinnamaldehyde oxime (1).
Figure 3: Conversion of cinnamaldehyde oxime (1, 25 µM in acetonitrile) by continuously running the catalytic...
Diastereoselective synthesis of nitroso acetals from (S,E)-γ-aminated nitroalkenes via multicomponent [4 + 2]/[3 + 2] cycloadditions promoted by LiCl or LiClO4
- Leandro Lara de Carvalho,
- Robert Alan Burrow and
- Vera Lúcia Patrocinio Pereira
Beilstein J. Org. Chem. 2013, 9, 838–845, doi:10.3762/bjoc.9.96
- the Lewis acid catalysis by cation–substrate interaction have been utilized to explain this enhancement of the reaction rate [12][13][14]. In the case of nitroalkene cycloadditions, performed in the presence of a Lewis acid, it is well documented that the rate acceleration effect caused by the Lewis
Graphical Abstract
Scheme 1: Reactivity of nitroalkenes and/or their respective nitronates in cycloaddition reactions.
Scheme 2: Synthetic route toward the chiral (S,E)-γ-aminated nitroalkenes 5a–c and their 1,3-diamine derivati...
Figure 1: ORTEP for nitroso acetal 11b.
Figure 2: 1D NOESY correlation between H2, H3a, H4 and H6 for all nitroso acetals.
Scheme 3: Transition-state models to stereoselective approaches in the multicomponent cycloadditions of 5a–c.
Scheme 4: Hydrogenolysis of 9c to pyrrolizidin-3-one 14c.
- -molecular-weight organic compounds, in which a metal is not part of the active principle. Organocatalysts donate or remove electrons or protons as their activation mode, hence defining four distinct subareas: Lewis base and Lewis acid catalysis on the one hand, and Brønsted base and Brønsted acid catalysis
Two-directional synthesis as a tool for diversity-oriented synthesis: Synthesis of alkaloid scaffolds
- Kieron M. G. O’Connell,
- Monica Díaz-Gavilán,
- Warren R. J. D. Galloway and
- David R. Spring
Beilstein J. Org. Chem. 2012, 8, 850–860, doi:10.3762/bjoc.8.95
- particular reference to the synthesis of polycyclic alkaloid scaffolds. Keywords: alkaloids; cascade reactions; chemical diversity; diversity-oriented synthesis; Lewis acid catalysis; two-directional synthesis; Introduction Diversity-oriented synthesis (DOS) aims to prepare structurally diverse compound
Graphical Abstract
Figure 1: Overview of the DOS strategy.
Scheme 1: Synthesis of linear cyclisation precursors 1–4.
Scheme 2: AlCl3 catalysed tandem Boc-removal/bicyclisation processes; the yields quoted refer to the isolated...
Scheme 3: (a) AlCl3 catalysed formation of tricyclic alkaloid 10 along with an X-ray crystal structure of 10;...
Scheme 4: (a) Optimal conditions to obtain trans-8 and 10 and the control experiments carried out to probe th...
Scheme 5: DOS of 5-5-6 and 5-6-6 tricyclic alkaloids 13 and 14.
Scheme 6: Total synthesis of myrrhine, epi-myrrhine and myrrhine-N-oxide.
Scheme 7: Use of nitromethane in DOS: Synthesis of meso-diphenylpyrrolidizine 17.
Scheme 8: Use of Tris as a substrate for DOS: Synthesis of decorated morpholines 22 and 23.
An intramolecular inverse electron demand Diels–Alder approach to annulated α-carbolines
- Zhiyuan Ma,
- Feng Ni,
- Grace H. C. Woo,
- Sie-Mun Lo,
- Philip M. Roveto,
- Scott E. Schaus and
- John K. Snyder
Beilstein J. Org. Chem. 2012, 8, 829–840, doi:10.3762/bjoc.8.93
- cycloaddition of 17a. Preparation of N-protected isatin-derived 1,2,4-triazines 8.a Lewis acid catalysis of amidation of triazine 8a.a IEDDA reaction conditions of 13a to give cycloadduct 14a.a Amidation-IEDDA sequence to α-carbolines 14 from triazine 8a.a Library synthesis matrix.a Supporting Information
Graphical Abstract
Figure 1: Natural products with α-carboline subunits.
Scheme 1: Retrosynthetic inverse electron Diels–Alder approach to α-carbolines.
Scheme 2: Condensation of isatins with ethyl oxaloamidrazonate to form triazines.
Scheme 3: Amidation of triazine ester 8a.
Scheme 4: Microwave-promoted IEDDA reaction of isatin derived triazines.
Scheme 5: One-pot amidation/cycloaddition of triazine ester 8a.
Scheme 6: Amidation/cycloaddition forming α-carbolines 14.
Scheme 7: Intramolecular hydrogen bonding prevents IEDDA cycloaddition of 14b.
Scheme 8: Preparation of unprotected triazine 15, and its lack of reactivity in cycloadditions.
Scheme 9: Transesterification and subsequent cycloaddition of 17a.
A practical route to tertiary diarylmethylamides or -carbamates from imines, organozinc reagents and acyl chlorides or chloroformates
- Erwan Le Gall,
- Antoine Pignon and
- Thierry Martens
Beilstein J. Org. Chem. 2011, 7, 997–1002, doi:10.3762/bjoc.7.112
- -substituted aldimines, formed in situ upon reaction of primary amines with aromatic aldehydes, cannot be undertaken under our established conditions. Thus, we intended to activate the C=N double bond by rendering the carbon more electrophilic and we initially envisaged the use of Lewis acid catalysis. Indeed
Graphical Abstract
Scheme 1: Addition of nucleophiles onto activated imines (A) or iminiums (B).
Scheme 2: Activation of the aldimine with MsCl.
An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals
- Marcus Baumann,
- Ian R. Baxendale,
- Steven V. Ley and
- Nikzad Nikbin
Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57
- an α-bromo ketone and an excess of aniline to give a 2-arylindole derivative 110 [31] (Scheme 24). For a long time this procedure has received little attention due to the requirement for rather extreme reaction conditions. However, the use of microwave radiation in combination with Lewis acid
- catalysis allows the reaction to be conducted much more efficiently [32]. This gives mid range yields (50–70%) of the 2-arylindoles over the two step sequence and tolerates a selection of functional groups on the aniline ring. Fluvastatin (2, Lescol), a HMG-CoA reductase inhibitor was initially prepared by
Graphical Abstract
Figure 1: Structures of atorvastatin and other commercial statins.
Figure 2: Structure of compactin.
Scheme 1: Synthesis of pentasubstituted pyrroles.
Scheme 2: [3 + 2] Cycloaddition to prepare 5-isopropylpyrroles.
Scheme 3: Regiospecific [3 + 2] cycloaddition to prepare the pyrrole scaffold.
Scheme 4: Formation of the pyrrole core of atorvastatin via [3 + 2] cycloaddition.
Scheme 5: Formation of pyrrole 33 via the Paal–Knorr reaction.
Scheme 6: Convergent synthesis towards atorvastatin.
Figure 3: Binding pocket of sunitinib in the TRK KIT.
Scheme 7: Synthesis of sunitinib.
Scheme 8: Alternative synthesis of sunitinib.
Scheme 9: Key steps in the syntheses of sumatriptan and zolmitriptan.
Scheme 10: Introduction of the N,N-dimethylaminoethyl side chain.
Scheme 11: Japp–Klingemann reaction in the synthesis of sumatriptan.
Scheme 12: Synthesis of the intermediate sulfonyl chlorides 62 and 63.
Scheme 13: Alternative introduction of the sulfonamide.
Scheme 14: Negishi-type coupling to benzylic sulfonamides.
Scheme 15: Heck reaction used to introduce the sulfonamide side chain of naratriptan.
Scheme 16: Synthesis of the oxazolinone appendage of zolmitriptan.
Scheme 17: Grandberg indole synthesis used in the preparation of rizatriptan.
Scheme 18: Improved synthesis of rizatriptan.
Scheme 19: Larock-type synthesis of rizatriptan.
Scheme 20: Synthesis of eletriptan.
Scheme 21: Heck coupling for the indole system in eletriptan.
Scheme 22: Attempted Fischer indole synthesis of elatriptan.
Scheme 23: Successful Fischer indole synthesis for eletriptan.
Scheme 24: Mechanistic rationale for the Bischler–Möhlau reaction.
Scheme 25: Bischler-type indole synthesis used in the fluvastatin sodium synthesis.
Scheme 26: Palladium-mediated synthesis of ondansetron.
Scheme 27: Fischer indole synthesis of ondansetron.
Scheme 28: Optimised Pictet–Spengler reaction towards tadalafil.
Figure 4: Structures of carvedilol 136 and propranolol 137.
Scheme 29: Synthesis of the carbazole core of carvedilol.
Scheme 30: Alternative syntheses of 4-hydroxy-9H-carbazole.
Scheme 31: Convergent synthesis of etodolac.
Scheme 32: Alternative synthesis of etodolac.
Figure 5: Structures of imidazole-containing drugs.
Scheme 33: Synthesis of functionalised imidazoles towards losartan.
Scheme 34: Direct synthesis of the chlorinated imidazole in losartan.
Scheme 35: Synthesis of trisubstituted imidazoles.
Scheme 36: Preparation of the imidazole ring in olmesartan.
Scheme 37: Synthesis of ondansetron.
Scheme 38: Alternative route to ondansetron and its analogues.
Scheme 39: Proton pump inhibitors and synthesis of esomeprazole.
Scheme 40: Synthesis of benzimidazole core pantoprazole.
Figure 6: Structure of rabeprazole 194.
Scheme 41: Synthesis of candesartan.
Scheme 42: Alternative access to the candesartan key intermediate 216.
Scheme 43: .Medicinal chemistry route to telmisartan.
Scheme 44: Improved synthesis of telmisartan.
Scheme 45: Synthesis of zolpidem.
Scheme 46: Copper-catalysed 3-component coupling towards zolpidem.
Figure 7: Structure of celecoxib.
Scheme 47: Preparation of celecoxib.
Scheme 48: Alternative synthesis of celecoxib.
Scheme 49: Regioselective access to celecoxib.
Scheme 50: Synthesis of pazopanib.
Scheme 51: Syntheses of anastrozole, rizatriptan and letrozole.
Scheme 52: Regioselective synthesis of anastrozole.
Scheme 53: Triazine-mediated triazole formation towards anastrozole.
Scheme 54: Alternative routes to 1,2,4-triazoles.
Scheme 55: Initial synthetic route to sitagliptin.
Figure 8: Binding of sitagliptin within DPP-IV.
Scheme 56: The process route to sitagliptin key intermediate 280.
Scheme 57: Synthesis of maraviroc.
Scheme 58: Synthesis of alprazolam.
Scheme 59: The use of N-nitrosoamidine derivatives in the preparation of fused benzodiazepines.
Figure 9: Structures of itraconazole, ravuconazole and voriconazole.
Scheme 60: Synthesis of itraconazole.
Scheme 61: Synthesis of rufinamide.
Scheme 62: Representative tetrazole formation in valsartan.
Figure 10: Structure of tetrazole containing olmesartan, candesartan and irbesartan.
Scheme 63: Early stage introduction of the tetrazole in losartan.
Scheme 64: Synthesis of cilostazol.
Figure 11: Structure of cefdinir.
Scheme 65: Semi-synthesis of cefdinir.
Scheme 66: Thiazole syntheses towards ritonavir.
Scheme 67: Synthesis towards pramipexole.
Scheme 68: Alternative route to pramipexole.
Scheme 69: Synthesis of famotidine.
Scheme 70: Efficient synthesis of the hyperuricemic febuxostat.
Scheme 71: Synthesis of ziprasidone.
Figure 12: Structure of mometasone.
Scheme 72: Industrial access to 2-furoic acid present in mometasone.
Scheme 73: Synthesis of ranitidine from furfuryl alcohol.
Scheme 74: Synthesis of nitrofurantoin.
Scheme 75: Synthesis of benzofuran.
Scheme 76: Synthesis of amiodarone.
Scheme 77: Synthesis of raloxifene.
Scheme 78: Alternative access to the benzo[b]thiophene core of raloxifene.
Scheme 79: Gewald reaction in the synthesis of olanzapine.
Scheme 80: Alternative synthesis of olanzapine.
Figure 13: Access to simple thiophene-containing drugs.
Scheme 81: Synthesis of clopidogrel.
Scheme 82: Pictet–Spengler reaction in the preparation of tetrahydrothieno[3,2-c]pyridine (422).
Scheme 83: Alternative synthesis of key intermediate 422.
Figure 14: Co-crystal structures of timolol (left) and carazolol (right) in the β-adrenergic receptor.
Scheme 84: Synthesis of timolol.
Scheme 85: Synthesis of tizanidine 440.
Scheme 86: Synthesis of leflunomide.
Scheme 87: Synthesis of sulfamethoxazole.
Scheme 88: Synthesis of risperidone.
Figure 15: Relative abundance of selected transformations.
Figure 16: The abundance of heterocycles within top 200 drugs (5-membered rings).
Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate
- Michael North and
- Marta Omedes-Pujol
Beilstein J. Org. Chem. 2010, 6, 1043–1055, doi:10.3762/bjoc.6.119
- Lewis base catalysis is dominant; and b) when Lewis acid catalysis is dominant. Hammett correlations with catalyst 2 at 0 °C. Data in red are obtained in dichloromethane [52], whilst data in blue are obtained in propylene carbonate. Synthesis and transformation of nonracemic silyl-protected cyanohydrins
Graphical Abstract
Scheme 1: Synthesis and transformation of nonracemic silyl-protected cyanohydrins.
Figure 1: Highly active metal(salen) complexes for asymmetric cyanohydrin synthesis.
Scheme 2: Synthesis of cyclic carbonates.
Scheme 3: Synthesis of cyanohydrin trimethylsilyl ethers and acetates.
Scheme 4: Equilibrium between bimetallic and monometallic Ti(salen) complexes.
Figure 2: Second-order kinetics plot for the addition of TMSCN to benzaldehyde at 0 °C catalysed by complex 2...
Figure 3: Plot of k2obs against [2], showing that the reactions are first order with respect to the concentratio...
Figure 4: Eyring plot to determine the activation parameters for catalyst 2 in propylene carbonate. The red a...
Figure 5: 51V NMR spectra of complex 2 recorded at 50 °C. a) Spectrum in CDCl3; b) spectrum in CDCl3 with 500...
Figure 6: Structures consistent with the 51V NMR spectra.
Figure 7: Bimetallic aluminium(salen) complex for asymmetric cyanohydrin synthesis.
Figure 8: Rate determining transition states for asymmetric cyanohydrin synthesis: a) when Lewis base catalys...
Figure 9: Hammett correlations with catalyst 2 at 0 °C. Data in red are obtained in dichloromethane [52], whilst ...
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
- –Crafts alkylation; green chemistry; hydroalkylation; hydroarylation; Lewis-acid catalysis; propargyl alcohols; Introduction In 1887 Charles Friedel and James Mason Crafts isolated amylbenzene after the treatment of amyl chloride with AlCl3 in benzene (Scheme 1) [1]. This was not only one of the first
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.
Recent progress on the total synthesis of acetogenins from Annonaceae
- Nianguang Li,
- Zhihao Shi,
- Yuping Tang,
- Jianwei Chen and
- Xiang Li
Beilstein J. Org. Chem. 2008, 4, No. 48, doi:10.3762/bjoc.4.48
Graphical Abstract
Scheme 1: Total synthesis of longifolicin by Marshall’s group.
Scheme 2: Total synthesis of corossoline by Tanaka’s group.
Scheme 3: Total synthesis of corossoline by Wu’s group.
Scheme 4: Total synthesis of pseudo-annonacin A by Hanessian’s group.
Scheme 5: Total synthesis of tonkinecin by Wu’s group.
Scheme 6: Total synthesis of gigantetrocin A by Shi’s group.
Scheme 7: Total synthesis of annonacin by Wu’s group.
Scheme 8: Total synthesis of solamin by Kitahara’s group.
Scheme 9: Total synthesis of solamin by Mioskowski’s group.
Scheme 10: Total synthesis of cis-solamin by Makabe’s group.
Scheme 11: Total synthesis of cis-solamin by Brown’s group.
Scheme 12: The formal synthesis of (+)-cis-solamin by Donohoe’s group.
Scheme 13: Total synthesis of cis-solamin by Stark’s group.
Scheme 14: Total synthesis of mosin B by Tanaka’s group.
Scheme 15: Total synthesis of longicin by Hanessian’s group.
Scheme 16: Total synthesis of murisolin and 16,19-cis-murisolin by Tanaka’s group.
Scheme 17: Synthesis of a stereoisomer library of (+)-murisolin by Curran’s group.
Scheme 18: Total synthesis of murisolin by Makabe’s group.
Scheme 19: Total synthesis of reticulatain-1 by Makabe’s group.
Scheme 20: Total synthesis of muricatetrocin C by Ley’s group.
Scheme 21: Total synthesis of (4R,12S,15S,16S,19R,20R,34S)-muricatetrocin (146) and (4R,12R,15S,16S,19R,20R,34S...
Scheme 22: Total synthesis of parviflorin by Hoye’s group.
Scheme 23: Total synthesis of parviflorin by Trost’s group.
Scheme 24: Total synthesis of trilobacin by Sinha’s group.
Scheme 25: Total synthesis of 15-epi-annonin I 181b by Scharf’s group.
Scheme 26: Total synthesis of squamocin A and squamocin D by Scharf’s group.
Scheme 27: Total synthesis of asiminocin by Marshall’s group.
Scheme 28: Total synthesis of asiminecin by Marshall’s group.
Scheme 29: Total synthesis of (+)-(30S)-bullanin by Marshall’s group.
Scheme 30: Total synthesis of uvaricin by the group of Sinha and Keinan.
Scheme 31: Formal synthesis of uvaricin by Burke’s group.
Scheme 32: Total synthesis of trilobin by Marshall’s group.
Scheme 33: Total synthesis of trilobin by the group of Sinha and Keinan.
Scheme 34: Total synthesis of asimilobin by the group of Wang and Shi.
Scheme 35: Total synthesis of squamotacin by the group of Sinha and Keinan.
Scheme 36: Total synthesis of asimicin by Marshall’s group.
Scheme 37: Total synthesis of asimicin by the group of Sinha and Keinan.
Scheme 38: Total synthesis of asimicin by Roush’s group.
Scheme 39: Total synthesis of asimicin by Marshall’s group.
Scheme 40: Total synthesis of 10-hydroxyasimicin by Ley’s group.
Scheme 41: Total synthesis of asimin by Marshall’s group.
Scheme 42: Total synthesis of bullatacin by the group of Sinha and Keinan.
Scheme 43: Total synthesis of bullatacin by Roush’s group.
Scheme 44: Total synthesis of bullatacin by Pagenkopf’s group.
Scheme 45: Total synthesis of rollidecins C and D by the group of Sinha and Keinan.
Scheme 46: Total synthesis of 30(S)-hydroxybullatacin by Marshall’s group.
Scheme 47: Total synthesis of uvarigrandin A and 5(R)-uvarigrandin A by Marshall’s group.
Scheme 48: Total synthesis of membranacin by Brown’s group.
Scheme 49: Total synthesis of membranacin by Lee’s group.
Scheme 50: Total synthesis of rolliniastatin 1 and rollimembrin by Lee’s group.
Scheme 51: Total synthesis of longimicin D by the group of Maezaki and Tanaka.
Scheme 52: Total synthesis of the structure proposed for mucoxin by Borhan’s group.
Scheme 53: Modular synthesis of adjacent bis-THF annonaceous acetogenins by Marshall’s group.
Scheme 54: Total synthesis of 4-deoxygigantecin by Tanaka’s group.
Scheme 55: Total synthesis of squamostatins D by Marshall’s group.
Scheme 56: Total synthesis of gigantecin by Crimmins’s group.
Scheme 57: Total synthesis of gigantecin by Hoye’s group.
Scheme 58: Total synthesis of cis-sylvaticin by Donohoe’s group.
Scheme 59: Total synthesis of 17(S),18(S)-goniocin by Sinha’s group.
Scheme 60: Total synthesis of goniocin and cyclogoniodenin T by the group of Sinha and Keinan.
Scheme 61: Total synthesis of jimenezin by Takahashi’s group.
Scheme 62: Total synthesis of jimenezin by Lee’s group.
Scheme 63: Total synthesis of jimenezin by Hoffmann’s group.
Scheme 64: Total synthesis of muconin by Jacobsen’s group.
Scheme 65: Total synthesis of (+)-muconin by Kitahara’s group.
Scheme 66: Total synthesis of muconin by Takahashi’s group.
Scheme 67: Total synthesis of muconin by the group of Yoshimitsu and Nagaoka.
Scheme 68: Total synthesis of mucocin by the group of Sinha and Keinan.
Scheme 69: Total synthesis of mucocin by Takahashi’s group.
Scheme 70: Total synthesis of (−)-mucocin by Koert’s group.
Scheme 71: Total synthesis of mucocin by the group of Takahashi and Nakata.
Scheme 72: Total synthesis of mucocin by Evans’s group.
Scheme 73: Total synthesis of mucocin by Mootoo’s group.
Scheme 74: Total synthesis of (−)-mucocin by Crimmins’s group.
Scheme 75: Total synthesis of pyranicin by the group of Takahashi and Nakata.
Scheme 76: Total synthesis of pyranicin by Rein’s group.
Scheme 77: Total synthesis of proposed pyragonicin by the group of Takahashi and Nakata.
Scheme 78: Total synthesis of pyragonicin by Rein’s group.
Scheme 79: Total synthesis of pyragonicin by Takahashi’s group.
Scheme 80: Total synthesis of squamostanal A by Figadère’s group.
Scheme 81: Total synthesis of diepomuricanin by Tanaka’s group.
Scheme 82: Total synthesis of (−)-muricatacin [(R,R)-373a] and its enantiomer (+)-muricatacin [(S,S)-373b] by ...
Scheme 83: Total synthesis of epi-muricatacin (+)-(S,R)-373c and (−)-(R,S)-373d by Scharf’s group.
Scheme 84: Total synthesis of (−)-muricatacin 373a and 5-epi-(−)-muricatacin 373d by Uang’s group.
Scheme 85: Total synthesis of four stereoisomers of muricatacin by Yoon’s group.
Scheme 86: Total synthesis of (+)-muricatacin by Figadère’s group.
Scheme 87: Total synthesis of (+)-epi-muricatacin and (−)-muricatacin by Couladouros’s group.
Scheme 88: Total synthesis of muricatacin by Trost’s group.
Scheme 89: Total synthesis of (−)-(4R,5R)-muricatacin by Heck and Mioskowski’s group.
Scheme 90: Total synthesis of muricatacin (−)-373a by the group of Carda and Marco.
Scheme 91: Total synthesis of (−)- and (+)-muricatacin by Popsavin’s group.
Scheme 92: Total synthesis of (−)-muricatacin by the group of Bernard and Piras.
Scheme 93: Total synthesis of (−)-muricatacin by the group of Yoshimitsu and Nagaoka.
Scheme 94: Total synthesis of (−)-muricatacin by Quinn’s group.
Scheme 95: Total synthesis of montecristin by Brückner’s group.
Scheme 96: Total synthesis of (−)-acaterin by the group of Franck and Figadère.
Scheme 97: Total synthesis of (−)-acaterin by Singh’s group.
Scheme 98: Total synthesis of (−)-acaterin by Kumar’s group.
Scheme 99: Total synthesis of rollicosin by Quinn’s group.
Scheme 100: Total synthesis of Rollicosin by Makabe’s group.
Scheme 101: Total synthesis of squamostolide by Makabe’s group.
Scheme 102: Total synthesis of tonkinelin by Makabe’s group.
Allylsilanes in the synthesis of three to seven membered rings: the silylcuprate strategy
- Asunción Barbero,
- Francisco J. Pulido and
- M. Carmen Sañudo
Beilstein J. Org. Chem. 2007, 3, No. 16, doi:10.1186/1860-5397-3-16
- under Lewis acid catalysis. [10] Thus, silicon assisted cyclization of oxoallylsilanes 3–8 in the presence of TiCl4 or EtAlCl2 results in the formation of 3-methylene-1-cyclopentanols 11–14 with a high degree of stereocontrol (Scheme 3). [7] The cis stereochemistry observed in 11 might indicate a
Graphical Abstract
Scheme 1: The silylcupration of allenes.
Scheme 2: Silylcupration of 1,2-propadiene and reaction with oxo compounds.
Scheme 3: Silicon assisted cyclization of oxoallylsilanes.
Scheme 4: Silylcupration of terminal alkynes bearing electron-withdrawing functions.
Scheme 5: The acid-catalyzed cyclization of epoxyallylsilanes.
Scheme 6: Intramolecular cyclization of TMS-epoxyallylsilanes.
Scheme 7: Spiro-cyclopropanation from oxoallylsilanes.
Scheme 8: Cyclobutane formation from hydroxy-functionalized allysilanes.
Scheme 9: Cyclobutene formation from vinyltin cuprates and epoxides.
Scheme 10: Silylcupration of 1,2-propadiene and reaction with α,β-unsaturated nitriles.
Scheme 11: Cycloheptane formation from silylcupration of α,β-unsaturated imines.
Scheme 12: Seven membered ring formation from functionalized allylsilanes.
