Search results
Search for "monoperoxyphthalate" in Full Text gives 7 result(s) in Beilstein Journal of Organic Chemistry.
Synthesis of ether lipids: natural compounds and analogues
- Marco Antônio G. B. Gomes,
- Alicia Bauduin,
- Chloé Le Roux,
- Romain Fouinneteau,
- Wilfried Berthe,
- Mathieu Berchel,
- Hélène Couthon and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96
Graphical Abstract
Figure 1: Chemical structure of some natural ether lipids (ELs).
Figure 2: Synthesis of lyso-PAF and PAF from 1-O-alkylglycerol [64].
Figure 3: Synthesis of lyso-PAF from 1,3-benzylideneglycerol 3.1 [69].
Figure 4: A) Synthesis of the two enantiomers of octadecylglycerol (4.6 and 4.10) from ᴅ-mannitol (4.1); B) s...
Figure 5: Four-step synthesis of PAF 5.6 from (S)-glycidol [73].
Figure 6: Synthesis of 1-O-alkylglycerol A) from solketal, B) from ᴅ- or ʟ-tartaric acid and the intermediate ...
Figure 7: Synthesis of EL building blocks starting from substituted glycidol 7.1a–c [82].
Figure 8: Synthesis of PAF 8.5 by using phosphoramidite 8.2 [86].
Figure 9: Synthesis of oleyl-PAF 9.7 from ʟ-serine [88].
Figure 10: Synthesis of racemic analogues of lyso-PAF 10.8 and PAF 10.9 featuring a phenyl group between the g...
Figure 11: Synthesis of racemic deoxy-lyso-PAF 11.7 and deoxy-PAF 11.8 [91].
Figure 12: Synthesis of racemic thio-PAF 12.8 [93].
Figure 13: Racemic synthesis of 13.6 to illustrate the modification of the glycerol backbone by adding a methy...
Figure 14: Racemic synthesis of 14.5 as an illustration of the introduction of methyl substituents on the glyc...
Figure 15: Synthesis of functionalized sn-2-acyl chains of PC-EL; A) Steglich esterification or acylation reac...
Figure 16: Synthesis of racemic mc-PAF (16.3), a carbamate analogue of PAF [102].
Figure 17: A) Synthesis of (R)-17.2 and (S)-17.6 starting from (S)-solketal (17.1); B) synthesis of N3-PAF (17...
Figure 18: Modification of the phosphocholine polar head to produce PAF analogues [81].
Figure 19: Racemic PAF analogues 19.3 and 19.5 characterized by the absence of the phosphate group [107].
Figure 20: Synthesis of PIP3-PAF (20.7) [108].
Figure 21: Large-scale synthesis of C18-edelfosine (21.8) [116].
Figure 22: Synthesis of C16-edelfosine (22.10) starting from isopropylidene-ʟ-glyceric acid methyl ester (22.1...
Figure 23: Phosphocholine moiety installation by the use of chlorophosphite 23.2 as key reagent [119].
Figure 24: Synthesis of rac-1-alkyl-2-O-methylglycerol (AMG) [120].
Figure 25: Synthesis of stereocontrolled 1-alkyl-2-O-methyl glycerol 25.9 (AMG) from dimethyl ᴅ-tartrate [81].
Figure 26: A) Racemic synthesis of thioether 26.4 [129,130], B) structure of sulfone analogue 26.5 [129].
Figure 27: Stereocontrolled synthesis of C18-edelfosine thioether analogue 27.8 [118].
Figure 28: Synthesis of thioether 28.4 that include a thiophosphate function [134].
Figure 29: Synthesis of ammonium thioether 29.4 and 29.6 [135].
Figure 30: Synthesis of the N-methylamino analogue of edelfosine 30.6 (BN52211) [138].
Figure 31: Synthesis of 1-desoxy analogues of edelfosine; A) with a saturated alkyl chain; B) synthesis of the...
Figure 32: Stereocontrolled synthesis of edelfosine analogue (S)-32.8 featuring a C18:1 lipid chain [142].
Figure 33: Synthesis of edelfosine analogues with modulation of the lipid chain; A) illustration with the synt...
Figure 34: Synthesis of phospholipid featuring a carbamate function to link the lipid chain to the glycerol un...
Figure 35: Synthesis of sesquiterpene conjugates of phospho glycero ether lipids [148].
Figure 36: Racemic synthesis of methyl-substituted glycerol analogues 36.7 and 36.10: A) synthesis of diether ...
Figure 37: Racemic synthesis of ilmofosine (37.6) [155,156].
Figure 38: A) Stereoselective synthesis of 38.5 via a stereoselective hydroboration reaction; B) synthesis of ...
Figure 39: Racemic synthesis of SRI62-834 (39.6) featuring a spiro-tetrahydrofurane heterocycle in position 2 ...
Figure 40: Racemic synthesis of edelfosine analogue 40.5 featuring an imidazole moiety in sn-2 position [160].
Figure 41: Racemic synthesis of fluorine-functionalized EL: A) Synthesis of 41.6 and B) synthesis of 41.8 [161-163].
Figure 42: A) Synthesis of the β-keto-ester 42.6 that also features a decyl linker between the phosphate and t...
Figure 43: Synthesis of phosphonate-based ether lipids; A) edelfosine phosphonate analogue 43.7 and B) thioeth...
Figure 44: Enantioselective synthesis of phosphonates 44.3 and 44.4 [171].
Figure 45: Racemic synthesis of phosphinate-based ether lipid 45.10 [172].
Figure 46: Racemic synthesis of edelfosine arsonium analogue 46.5 [173].
Figure 47: Synthesis of edelfosine dimethylammonium analogue 47.2 [118].
Figure 48: Synthesis of rac-C18-edelfosine methylammonium analogue 48.4 [176].
Figure 49: A) Synthesis of edelfosine N-methylpyrrolidinium analogue 49.2 or N-methylmorpholinium analogue 49.3...
Figure 50: A) Synthesis of edelfosine’s analogue 50.4 with a PE polar group; B) illustration of a pyridinium d...
Figure 51: A) Synthesis of 51.4 featuring a thiazolium cationic moiety; B) synthesis of thiazolium-based EL 51...
Figure 52: Synthesis of cationic ether lipids 52.3, 52.4 and 52.6 [135,183].
Figure 53: Synthesis of cationic carbamate ether lipid 53.5 [184].
Figure 54: Synthesis of cationic sulfonamide 54.5 [185].
Figure 55: Chemical structure of ONO-6240 (55.1) and SRI-63-119 (55.2).
Figure 56: Synthesis of non-ionic ether lipids 56.2–56.9 [188].
Figure 57: Synthesis of ether lipid conjugated to foscarnet 57.6 [189].
Figure 58: A) Synthesis of ether lipid conjugated to arabinofuranosylcytosine; B) synthesis of AZT conjugated ...
Figure 59: Synthesis of quercetin conjugate to edelfosine [191].
Figure 60: Synthesis of 60.8 (Glc-PAF) [194].
Figure 61: A) Synthesis of amino ether lipid 61.7 functionalized with a rhamnose unit and its amide analogue 6...
Figure 62: A) Synthesis of glucose ether lipid 62.4; B) structure of ether lipid 62.5 possessing a maltose uni...
Figure 63: A) Synthesis of glucuronic methyl ester 63.8; B) structure of cellobiose 63.9 and maltose 63.10 ana...
Figure 64: A) Synthesis of maltosyl glycerolipid 64.7; B) structure of lactose analogue 64.8 prepared followin...
Figure 65: A) Asymmetric synthesis of the aglycone moiety starting from allyl 4-methoxyphenyl ether; B) glycos...
Figure 66: A) Synthesis of ohmline possessing a lactose moiety. B) Structure of other glyco glycero lipids pre...
Figure 67: A) Synthesis of lactose-glycerol ether lipid 67.5; B) analogues possessing a maltose (67.6) or meli...
Figure 68: Synthesis of digalactosyl EL 68.6, A) by using trityl, benzyl and acetyl protecting groups, B) by u...
Figure 69: A) Synthesis of α-ohmline; B) structure of disaccharide ether lipids prepared by using similar meth...
Figure 70: Synthesis of lactose ether lipid 70.3 and its analogue 70.6 featuring a carbamate function as linke...
Figure 71: Synthesis of rhamnopyranoside diether 71.4 [196].
Figure 72: Synthesis of 1-O-hexadecyl-2-O-methyl-3-S-(α-ᴅ-1'-thioglucopyranosyl)-sn-glycerol (72.5) [225].
Figure 73: A) Preparation of lipid intermediate 73.4; B) synthesis of 2-desoxy-C-glycoside 73.10 [226].
Figure 74: Synthesis of galactose-pyridinium salt 74.3 [228].
Figure 75: Synthesis of myo-inositol derivative Ino-C2-PAF (75.10) [230].
Figure 76: A) Synthesis of myo-inositol phosphate building block 76.7; B) synthesis of myo-inositolphosphate d...
Figure 77: A) Synthesis of phosphatidyl-3-desoxy-inositol 77.4; B) synthesis of phosphono-3-desoxyinositol 77.9...
Figure 78: A) Structure of diether phosphatidyl-myo-inositol-3,4-diphosphate 78.1; B) synthesis of phosphatidy...
Figure 79: A) Synthesis of diether-phosphatidyl derivative 79.4 featuring a hydroxymethyl group in place of a ...
Figure 80: Synthesis of Glc-amine-PAF [78].
Figure 81: Synthesis of glucosamine ether lipid 81.4 and its analogues functionalized in position 3 of the ami...
Figure 82: Synthesis of fully deprotected aminoglucoside ether lipid 82.5 [246].
Figure 83: Synthesis of C-aminoglycoside 83.12 using Ramberg–Bäcklund rearrangement as a key step [250].
Figure 84: A) List of the most important glyco lipids and amino glyco lipids included in the study of Arthur a...
Figure 85: Synthesis of mannosamine ether lipid 85.6 [254].
Figure 86: A) Synthesis of glucosamine ether lipids with a non-natural ʟ-glucosamine moiety; B) synthesis of e...
Figure 87: A) Structure of the most efficient anticancer agents 87.1–87.4 featuring a diamino glyco ether lipi...
Figure 88: A) Synthesis of diamino glyco ether lipid 87.4; B) synthesis of bis-glycosylated ether lipid 88.10 [256]....
Figure 89: Synthesis of triamino ether lipid 89.4 [260].
Figure 90: Synthesis of chlorambucil conjugate 90.7 [261].
Figure 91: Three main methods for the preparation of glycerol ether lipid 91.3; A) from solketal and via a tri...
Figure 92: Four different methods for the installation of the phosphocholine polar head group; A) method using...
Figure 93: Illustration of two methods for the installation of saccharides or aminosaccharides; A) O-glycosyla...
Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update
- Bin Yu,
- Hui Xing,
- De-Quan Yu and
- Hong-Min Liu
Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98
- yields (up to 99% yield, Scheme 42) [59]. Interestingly, treatment of the adducts with magnesium monoperoxyphthalate (MMPP) gave the corresponding azoxy compounds in excellent yields (up to 99%) and with complete regioselectivities and excellent enantioselectivities (up to 99% ee). A stereochemical model
Graphical Abstract
Figure 1: 3-Hydroxyoxindole-containing natural products and biologically active molecules.
Scheme 1: Chiral CNN pincer Pd(II) complex 1 catalyzed asymmetric allylation of isatins.
Scheme 2: Asymmetric allylation of ketimine catalyzed by the chiral CNN pincer Pd(II) complex 2.
Scheme 3: Pd/L1 complex-catalyzed asymmetric allylation of 3-O-Boc-oxindoles.
Scheme 4: Cu(OTf)2-catalyzed asymmetric direct addition of acetonitrile to isatins.
Scheme 5: Chiral tridentate Schiff base/Cu complex catalyzed asymmetric Friedel–Crafts alkylation of isatins ...
Scheme 6: Guanidine/CuI-catalyzed asymmetric alkynylation of isatins with terminal alkynes.
Scheme 7: Asymmetric intramolecular direct hydroarylation of α-ketoamides.
Scheme 8: Plausible catalytic cycle for the direct hydroarylation of α-ketoamides.
Scheme 9: Ir-catalyzed asymmetric arylation of isatins with arylboronic acids.
Scheme 10: Enantioselective decarboxylative addition of β-ketoacids to isatins.
Scheme 11: Ruthenium-catalyzed hydrohydroxyalkylation of olefins and 3-hydroxy-2-oxindoles.
Scheme 12: Proposed catalytic mechanism and stereochemical model.
Scheme 13: In-catalyzed allylation of isatins with stannylated reagents.
Scheme 14: Modified protocol for the synthesis of allylated 3-hydroxyoxindoles.
Scheme 15: Hg-catalyzed asymmetric allylation of isatins with allyltrimethylsilanes.
Scheme 16: Enantioselective additions of organoborons to isatins.
Scheme 17: Asymmetric aldol reaction of isatins with cyclohexanone.
Scheme 18: Enantioselective aldol reactions of aliphatic aldehydes with isatin derivatives and the plausible t...
Scheme 19: Enantioselective aldol reaction of isatins and 2,2-dimethyl-1,3-dioxan-5-one.
Scheme 20: Asymmetric aldol reactions between ketones and isatins.
Scheme 21: Phenylalanine lithium salt-catalyzed asymmetric synthesis of 3-alkyl-3-hydroxyoxindoles.
Scheme 22: Aldolization between isatins and dihydroxyacetone derivatives.
Scheme 23: One-pot asymmetric synthesis of convolutamydine A.
Scheme 24: Asymmetric aldol reactions of cyclohexanone and acetone with isatins.
Scheme 25: Aldol reactions of acetone with isatins.
Scheme 26: Aldol reactions of ketones with isatins.
Scheme 27: Enantioselective allylation of isatins.
Scheme 28: Asymmetric aldol reaction of trifluoromethyl α-fluorinated β-keto gem-diols with isatins.
Scheme 29: Plausible mechanism proposed for the asymmetric aldol reaction.
Scheme 30: Asymmetric aldol reaction of 1,1-dimethoxyacetone with isatins.
Scheme 31: Enantioselective Friedel-Crafts reaction of phenols with isatins.
Scheme 32: Enantioselective addition of 1-naphthols with isatins.
Scheme 33: Enantioselective aldol reaction between 3-acetyl-2H-chromen-2-ones and isatins.
Scheme 34: Stereoselective Mukaiyama–aldol reaction of fluorinated silyl enol ethers with isatins.
Scheme 35: Asymmetric vinylogous Mukaiyama–aldol reaction between 2-(trimethylsilyloxy)furan and isatins.
Scheme 36: β-ICD-catalyzed MBH reactions of isatins with maleimides.
Scheme 37: β-ICD-catalyzed MBH reactions of 7-azaisatins with maleimides and activated alkenes.
Scheme 38: Enantioselective aldol reaction of isatins with ketones.
Scheme 39: Direct asymmetric vinylogous aldol reactions of allyl ketones with isatins.
Scheme 40: Enantioselective aldol reactions of ketones with isatins.
Scheme 41: The MBH reaction of isatins with α,β-unsaturated γ-butyrolactam.
Scheme 42: Reactions of tert-butyl hydrazones with isatins followed by oxidation.
Scheme 43: Aldol reactions of isatin derivatives with ketones.
Scheme 44: Enantioselective decarboxylative cyanomethylation of isatins.
Scheme 45: Catalytic kinetic resolution of 3-hydroxy-3-substituted oxindoles.
Scheme 46: Lewis acid catalyzed Friedel–Crafts alkylation of 3-hydroxy-2-oxindoles with electron-rich phenols.
Scheme 47: Lewis acid catalyzed arylation of 3-hydroxyoxindoles with aromatics.
Scheme 48: Synthetic application of 3-arylated disubstituted oxindoles in the construction of core structures ...
Scheme 49: CPA-catalyzed dearomatization and arylation of 3-indolyl-3-hydroxyoxindoles with tryptamines and 3-...
Scheme 50: CPA-catalyzed enantioselective decarboxylative alkylation of β-keto acids with 3-hydroxy-3-indolylo...
Scheme 51: BINOL-derived imidodiphosphoric acid-catalyzed enantioselective Friedel–Crafts reactions of indoles...
Scheme 52: CPA-catalyzed enantioselective allylation of 3-indolylmethanols.
Scheme 53: 3-Indolylmethanol-based substitution and cycloaddition reactions.
Scheme 54: CPA-catalyzed asymmetric [3 + 3] cycloaddtion reactions of 3-indolylmethanols with azomethine ylide...
Scheme 55: CPA-catalyzed three-component cascade Michael/Pictet–Spengler reactions of 3-indolylmethanols and a...
Scheme 56: Acid-promoted chemodivergent and stereoselective synthesis of diverse indole derivatives.
Scheme 57: CPA-catalyzed asymmetric formal [3 + 2] cycloadditions.
Scheme 58: CPA-catalyzed enantioselective cascade reactions for the synthesis of C7-functionlized indoles.
Scheme 59: Lewis acid-promoted Prins cyclization of 3-allyl-3-hydroxyoxindoles with aldehydes.
Scheme 60: Ga(OTf)3-catalyzed reactions of allenols and phenols.
Scheme 61: I2-catalyzed construction of pyrrolo[2.3.4-kl]acridines from enaminones and 3-indolyl-3-hydroxyoxin...
Scheme 62: CPA-catalyzed asymmetric aza-ene reaction of 3-indolylmethanols with cyclic enaminones.
Scheme 63: Asymmetric α-alkylation of aldehydes with 3-indolyl-3-hydroxyoxindoles.
Scheme 64: Organocatalytic asymmetric α-alkylation of enolizable aldehydes with 3-indolyl-3-hydroxyoxindoles a...
Selective allylic hydroxylation of acyclic terpenoids by CYP154E1 from Thermobifida fusca YX
- Anna M. Bogazkaya,
- Clemens J. von Bühler,
- Sebastian Kriening,
- Alexandrine Busch,
- Alexander Seifert,
- Jürgen Pleiss,
- Sabine Laschat and
- Vlada B. Urlacher
Beilstein J. Org. Chem. 2014, 10, 1347–1353, doi:10.3762/bjoc.10.137
- a procedure by Fringuelli et al. [39] nerol (2) was treated with magnesium monoperoxyphthalate (MPPA) in the presence of NaOH to give 2,3-epoxynerol (6) in 77% yield together with 20% of reisolated starting material 2 (see Supporting Information File 1). According to a method by McMurry [24
- hindrance were selected. Terpene substrates (grey background) and their oxidised derivatives. a) Ac2O, pyridine, room temperature, 24 h; b) SeO2, t-BuOOH, CH2Cl2, 0 °C, 5 h; c) K2CO3, MeOH, room temperature, 2.5 h; d) MPPA, NaOH, H2O, room temperature, 5 h (MPPA = magnesium monoperoxyphthalate). a) SeO2, t
Graphical Abstract
Figure 1: Immediate heme surroundings shown for the nearest relative of CYP154E1 with available crystal struc...
Scheme 1: Terpene substrates (grey background) and their oxidised derivatives.
Scheme 2: a) Ac2O, pyridine, room temperature, 24 h; b) SeO2, t-BuOOH, CH2Cl2, 0 °C, 5 h; c) K2CO3, MeOH, roo...
Scheme 3: a) SeO2, t-BuOOH, CH2Cl2, 0 °C, 3.5 h.
Magnesium bis(monoperoxyphthalate) hexahydrate as mild and efficient oxidant for the synthesis of selenones
- Andrea Temperini,
- Massimo Curini,
- Ornelio Rosati and
- Lucio Minuti
Beilstein J. Org. Chem. 2014, 10, 1267–1271, doi:10.3762/bjoc.10.127
- Abstract A new, efficient and mild method for the direct oxidation of selenides to selenones using magnesium bis(monoperoxyphthalate) hexahydrate (MMPP) has been developed. Noteworthy this transformation proceeds at room temperature, employs a cheap and safety oxidant and has a broad functional group
- tolerance. Moreover, the produced selenones could be useful intermediates for the synthesis of different heterocyclic compounds. Keywords: heterocycles; monoperoxyphthalate; oxidation; selenides; selenones; Introduction Organoselenium compounds have received considerable attention in recent times because
- investigated the use of magnesium bis(monoperoxyphthalate) hexahydrate (MMPP) as a new oxidant for the straightforward conversion of selenides 1 to selenones 2 under mild experimental conditions. Magnesium bis(monoperoxyphthalate) hexahydrate is a cheap commercially available, relatively stable and easy to use
Graphical Abstract
Scheme 1: General transformation of selenides to selenones.
Scheme 2: Phenylselenone 2 as useful leaving group for the synthesis of different organic molecules.
Polar reactions of acyclic conjugated bisallenes
- Reiner Stamm and
- Henning Hopf
Beilstein J. Org. Chem. 2013, 9, 36–48, doi:10.3762/bjoc.9.5
- protocol. The oxidation of these highly unsaturated compounds with magnesium monoperoxyphthalate (MMPP) results predominantly in the formation of cyclopentenone derivatives in a Nazarov-type cyclization. The addition of hydrohalides leads to halo-1,3,5-trienes whereas bromine and iodine addition furnish
Graphical Abstract
Scheme 1: The alkylated conjugated bisallenes 1– 3 as model systems for polar reactions.
Scheme 2: Alkylation and silylation of 2.
Scheme 3: Allylation of the monoanion 4.
Scheme 4: Metalation/silylation of hydrocarbon 3.
Scheme 5: Quenching of 4 with DMF and acetone.
Scheme 6: Further reactions of 2/4 with various electrophiles.
Scheme 7: Oxidation of conjugated bisallenes with different oxidizing agents according to [26].
Scheme 8: Oxidation of 2, 7 and 5 with MMPP.
Scheme 9: Oxidation of the asymmetric bisallene 3 by air.
Scheme 10: Epoxidation of the disilylbisallenes 11 and 12.
Scheme 11: The addition of HCl and HBr to the bisallenes 2 and 5.
Scheme 12: The addition of bromine to the bisallene 2.
Scheme 13: The addition of iodine to the conjugated bisallenes 61, 2 and 3.
Scheme 14: Addition of chlorosulfonyl isocyanate (CSI, 66) to allenes.
The chemistry of bisallenes
- Henning Hopf and
- Georgios Markopoulos
Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225
- bisoxygenated product 211 for which 209 appears to be the most reasonable precursor. The oxidation of 24 with magnesium monoperoxyphthalate provides 209 in 32% isolated yield [138]. Looking at the structures of starting material and product 209 the process resembles the Nazarov cyclization of divinyl ketones to
Graphical Abstract
Figure 1: Loschmidt’s structure proposal for benzene (1) (Scheme 181 from [3]) and the corresponding modern stru...
Figure 2: The first isolated bisallenes.
Figure 3: Carbon skeletons of selected bisallenes discussed in this review.
Scheme 1: The preparation of 1,2,4,5-hexatetraene (2).
Scheme 2: The preparation of a conjugated bisallene by the DMS-protocol.
Scheme 3: Preparation of the 3-deuterio- and 3,4-dideuterio derivatives of 24.
Scheme 4: A versatile method to prepare alkylated conjugated bisallenes and other allenes.
Scheme 5: A preparation of 3,4-dimethyl-1,2,4,5-hexatetraene (38).
Scheme 6: A (C6 + 0)-approach to 1,2,4,5-hexatetraene (2).
Scheme 7: The preparation of a fully alkylated bisallenes from a 2,4-hexadiyne-1,6-diol diacetate.
Scheme 8: The preparation of the first phenyl-substituted conjugated bisallenes 3 and 4.
Scheme 9: Selective hydrogenation of [5]cumulenes to conjugated bisallenes: another (C6 + 0)-route.
Scheme 10: Aryl-substituted conjugated bisallenes by a (C3 + C3)-approach.
Scheme 11: Hexaphenyl-1,2,4,5-hexatetraene (59) by a (C3 + C3)-approach.
Scheme 12: An allenation route to conjugated bisallenes.
Scheme 13: The preparation of 3,4-difunctionalized conjugated bisallenes.
Scheme 14: Problems during the preparation of sulfur-substituted conjugated bisallenes.
Scheme 15: The preparation of 3,4-dibromo bisallenes.
Scheme 16: Generation of allenolates by an oxy-Cope rearrangement.
Scheme 17: A linear trimerization of alkynes to conjugated bisallenes: a (C2 + C2 + C2)-protocol.
Scheme 18: Preparation of a TMS-substituted conjugated bisallene by a C3-dimerization route.
Scheme 19: A bis(trimethylsilyl)bisallene by a C3-coupling protocol.
Scheme 20: The rearrangement of highly substituted benzene derivatives into their conjugated bisallenic isomer...
Scheme 21: From fully substituted benzene derivatives to fully substituted bisallenes.
Scheme 22: From a bicyclopropenyl to a conjugated bisallene derivative.
Scheme 23: The conversion of a bismethylenecyclobutene into a conjugated bisallene.
Scheme 24: The preparation of monofunctionalized bisallenes.
Scheme 25: Preparation of bisallene diols and their cyclization to dihydrofurans.
Scheme 26: A 3,4-difunctionalized conjugated bisallene by a C3-coupling process.
Scheme 27: Preparation of a bisallenic diketone by a coupling reaction.
Scheme 28: Sulfur and selenium-substituted bisallenes by a [2.3]sigmatropic rearrangement.
Scheme 29: The biallenylation of azetidinones.
Scheme 30: The preparation of a fully ferrocenylated conjugated bisallene.
Scheme 31: The first isomerization of a 1,5-hexadiyne to a 1,2,4,5-hexatetraene.
Scheme 32: The preparation of alkynyl-substituted bisallenes by a C3-dimerization protocol.
Scheme 33: Preparation of another completely ferrocenylated bisallene.
Scheme 34: The cyclization of 1,5-hexadiyne (129) to 3,4-bismethylenecyclobutene (130) via 1,2,4,5-hexatetraen...
Scheme 35: Stereochemistry of the thermal cyclization of bisallenes to bismethylenecyclobutenes.
Scheme 36: Bisallene→bismethylenecyclobutene ring closures in the solid state.
Scheme 37: A bisallene cyclization/dimerization reaction.
Scheme 38: A selection of Diels–Alder additions of 1,2,4,5-hexatetraene with various double-bond dienophiles.
Scheme 39: The stereochemistry of the [2 + 4] cycloaddition to conjugated bisallenes.
Scheme 40: Preparation of azetidinone derivatives from conjugated bisallenes.
Scheme 41: Cycloaddition of heterodienophiles to a conjugated bisallene.
Scheme 42: Addition of triple-bond dienophiles to conjugated bisallenes.
Scheme 43: Sulfur dioxide addition to conjugated bisallenes.
Scheme 44: The addition of a germylene to a conjugated bisallene.
Scheme 45: Trapping of conjugated bisallenes with phosphinidenes.
Scheme 46: The cyclopropanantion of 1,2,4,5-hexatetraene (2).
Scheme 47: Photochemical reactions involving conjugated bisallenes.
Scheme 48: Base-catalyzed isomerizations of conjugated bisallenes.
Scheme 49: Ionic additions to a conjugated bisallene.
Scheme 50: Oxidation reactions of a conjugated bisallene.
Scheme 51: The mechanism of oxidation of the bisallene 24.
Scheme 52: CuCl-catalyzed cyclization of 1,2,4,5-hexatetraene (2).
Scheme 53: The conversion of conjugated bisallenes into cyclopentenones.
Scheme 54: Oligomerization of a conjugated bisallene by nickel catalysts.
Scheme 55: Generation of 1,2,5,6-heptatetraene (229) as a reaction intermediate.
Scheme 56: The preparation of a stable derivative of 1,2,5,6-heptatetraene.
Scheme 57: A bisallene with a carbonyl group as a spacer element.
Scheme 58: The first preparation of 1,2,6,7-octatetraene (242).
Scheme 59: Preparation of 1,2,6,7-octatetraenes by (C4 + C4)-coupling of enynes.
Scheme 60: Preparation of 1,2,6,7-octatetraenes by (C4 + C4)-coupling of homoallenyl bromides.
Scheme 61: Preparation of 1,2,6,7-octatetraenes by alkylation of propargylic substrates.
Scheme 62: Preparation of two highly functionalized 1,2,6,7-octatetraenes.
Scheme 63: Preparation of several higher α,ω-bisallenes.
Scheme 64: Preparation of different alkyl derivatives of α,ω-bisallenes.
Scheme 65: The preparation of functionalized 1,2,7,8-nonatetraene derivatives.
Scheme 66: Preparation of functionalized α,ω-bisallenes.
Scheme 67: The preparation of an α,ω-bisallene by direct homologation of an α,ω-bisalkyne.
Scheme 68: The gas-phase pyrolysis of 4,4-dimethyl-1,2,5,6-heptatetraene (237).
Scheme 69: Gas-phase pyrolysis of 1,2,6,7-octatetraene (242).
Scheme 70: The cyclopropanation of 1,2,6,7-octatetraene (242).
Scheme 71: Intramolecular cyclization of 1,2,6,7-octatetraene derivatives.
Scheme 72: The gas-phase pyrolysis of 1,2,7,8-nonatetraene (265) and 1,2,8,9-decatetraene (266).
Scheme 73: Rh-catalyzed cyclization of a functionalized 1,2,7,8-nonatetraene.
Scheme 74: A triple cyclization involving two different allenic substrates.
Scheme 75: Bicyclization of keto derivatives of 1,2,7,8-nonatetraene.
Scheme 76: The preparation of complex organic compounds from functionalized bisallenes.
Scheme 77: Cycloisomerization of an α,ω-bisallene containing a C9 tether.
Scheme 78: Organoborane polymers from α,ω-bisallenes.
Scheme 79: Preparation of trans- (337) and cis-1,2,4,6,7-octapentaene (341).
Scheme 80: The preparation of 4-methylene-1,2,5,6-heptatetraene (349).
Scheme 81: The preparation of acetylenic bisallenes.
Scheme 82: The preparation of derivatives of hydrocarbon 351.
Scheme 83: The construction of macrocyclic alleno-acetylenes.
Scheme 84: Preparation and reactions of 4,5-bismethylene-1,2,6,7-octatetraene (365).
Scheme 85: Preparation of 1,2-bis(propadienyl)benzene (370).
Scheme 86: The preparation of 1,4-bis(propadienyl)benzene (376).
Scheme 87: The preparation of aromatic and heteroaromatic bisallenes by metal-mediated coupling reactions.
Scheme 88: Double cyclization of an aromatic bisallene.
Scheme 89: Preparation of an allenic [15]paracyclophane by a ring-closing metathesis reaction of an aromatic α...
Scheme 90: Preparation of a macrocyclic ring system containing 1,4-bis(propadienyl)benzene units.
Scheme 91: Preparation of copolymers from 1,4-bis(propadienyl)benzene (376).
Scheme 92: A boration/copolymerization sequence of an aromatic bisallene and an aromatic bisacetylene.
Scheme 93: Formation of a layered aromatic bisallene.
Figure 4: The first members of the semicyclic bisallene series.
Scheme 94: Preparation of the first bis(vinylidene)cyclobutane derivative.
Scheme 95: Dimerization of strain-activated cumulenes to bis(vinylidene)cyclobutanes.
Scheme 96: Photodimerization of two fully substituted butatrienes in the solid state.
Scheme 97: Preparation of the two parent bis(vinylidene)cyclobutanes.
Scheme 98: The preparation of 1,3-bis(vinylidene)cyclopentane and its thermal isomerization.
Scheme 99: The preparation of the isomeric bis(vinylidene)cyclohexanes.
Scheme 100: Bi- and tricyclic conjugated bisallenes.
Scheme 101: A selection of polycyclic bisallenes.
Scheme 102: The first endocyclic bisallenes.
Figure 5: The stereochemistry of 1,2,6,7-cyclodecatetraene.
Scheme 103: The preparation of several endocyclic bisallenes.
Scheme 104: Synthesis of diastereomeric derivatives of 1,2,6,7-cyclodecatetraene.
Scheme 105: Preparation of a derivative of 1,2,8,9-cyclotetradecatetraene.
Scheme 106: The preparation of keto derivatives of cyclic bisallenes.
Scheme 107: The preparation of cyclic biscumulenic ring systems.
Scheme 108: Cyclic bisallenes in natural- and non-natural-product chemistry.
Scheme 109: The preparation of iron carbonyl complexes from cyclic bisallenes.
Figure 6: A selection of unknown exocyclic bisallenes that should have interesting chemical properties.
Scheme 110: The thermal isomerization of 1,2-diethynylcyclopropanes and -cyclobutanes.
Scheme 111: Intermediate generation of a cyclooctapentaene.
Scheme 112: Attempted preparation of a cyclodecahexaene.
Scheme 113: The thermal isomerization of 1,5,9-cyclododecatriyne (511) into [6]radialene (514).
Scheme 114: An isomerization involving a diketone derived from a conjugated bisallene.
Scheme 115: Typical reaction modes of heteroorganic bisallenes.
Scheme 116: Generation and thermal behavior of acyclic hetero-organic bisallenes.
Scheme 117: Generation of bis(propadienyl)thioether.
Scheme 118: The preparation of a bisallenic sulfone and its thermal isomerization.
Scheme 119: Bromination of the bisallenic sulfone 535.
Scheme 120: Metalation/hydrolysis of the bisallenic sulfone 535.
Scheme 121: Aromatic compounds from hetero bisallenes.
Scheme 122: Isomerization/cyclization of bispropargylic ethers.
Scheme 123: The preparation of novel aromatic systems by base-catalyzed isomerization of bispropargyl ethers.
Scheme 124: The isomerization of bisacetylenic thioethers to bicyclic thiophenes.
Scheme 125: Aromatization of macrocyclic bispropargylic sulfides.
Scheme 126: Preparation of ansa-compounds from macrocyclic bispropargyl thioethers.
Scheme 127: Alternate route for cyclization of a heterorganic bisallene.
Scheme 128: Multiple isomerization/cyclization of “double” bispropargylic thioethers.
Scheme 129: Preparation of a bisallenyl disulfide and its subsequent bicyclization.
Scheme 130: Thermal cyclization of a bisallenyl thiosulfonate.
Scheme 131: Some reactions of heteroorganic bisallenes with two sulfur atoms.
Scheme 132: Further methods for the preparation of heteroorganic bisallenes.
Scheme 133: Cyclization reactions of heteroorganic bisallenes.
Scheme 134: Thermal cycloadditions of bisallenic tertiary amines.
Scheme 135: Cyclization of a bisallenic tertiary amine in the presence of a transition-metal catalyst.
Scheme 136: A Pauson–Khand reaction of a bisallenic ether.
Scheme 137: Formation of a 2:1adduct from two allenic substrates.
Scheme 138: A ring-forming silastannylation of a bisallenic tertiary amine.
Scheme 139: A three-component cyclization involving a heterorganic bisallene.
Scheme 140: Atom-economic construction of a complex organic framework from a heterorganic α,ω-bisallene.
Efficient oxidation of oleanolic acid derivatives using magnesium bis(monoperoxyphthalate) hexahydrate (MMPP): A convenient 2-step procedure towards 12-oxo-28-carboxylic acid derivatives
- Jorge A. R. Salvador,
- Vânia M. Moreira,
- Rui M. A. Pinto,
- Ana S. Leal and
- José A. Paixão
Beilstein J. Org. Chem. 2012, 8, 164–169, doi:10.3762/bjoc.8.17
- /bjoc.8.17 Abstract A new, straightforward and high yielding procedure to convert oleanolic acid derivatives into the corresponding δ-hydroxy-γ-lactones, by using the convenient oxidizing agent magnesium bis(monoperoxyphthalate) hexahydrate (MMPP) in refluxing acetonitrile, is reported. In addition, a
- (monoperoxyphthalate) hexahydrate (MMPP) is commercially available, inexpensive and relatively stable [32][33][34] and has been used in the oxidation of various functional groups [35][36][37][38][39][40][41][42]. This oxidant is non-shock-sensitive and non-deflagrating [43]. Moreover, its use greatly simplifies the
Graphical Abstract
Figure 1: ORTEP diagram of compound 4 (50% probability level, H atoms of arbitrary sizes). The asymmetric uni...
Scheme 1: Sequential 2-step synthesis of 3,12-dioxoolean-28-oic acid (11) directly from 3-oxooleanolic acid (1...
Figure 2: ORTEP diagram of compound 11 (50% probability level, H atoms of arbitrary sizes).
