Search for "sensitizer" in Full Text gives 53 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2017, 13, 644–647, doi:10.3762/bjoc.13.63
Graphical Abstract
Scheme 1: Top: The natural product deoxynojirimycin and two analogues and marketed drugs Glyset and Zavesca. ...
Scheme 2: Synthesis of Boc- and Pht-protected diene substrates for endoperoxide synthesis. TBA-Cl = tetrabuty...
Scheme 3: Synthesis of endoperoxides 17–19 by [4 + 2]-cycloaddition of dienes 14–16 with singlet oxygen. The ...
Scheme 4: Dihydroxylation and protection of endoperoxides 18 and 19 to provide novel building blocks 20–23 fo...
Beilstein J. Org. Chem. 2016, 12, 1798–1811, doi:10.3762/bjoc.12.170
Graphical Abstract
Figure 1: The challenge of mixing the three dispersed entities gas, liquid, and light for photochemical appli...
Scheme 1: Mutual interdependencies of critical reaction and reactor parameters.
Scheme 2: Blueprint of the home-built microflow photoreactor; schematic illustration of the reactor setup wit...
Figure 2: Total absorbance of methylene blue solutions in acetonitrile according to the Beer-Lambert law: Eλ ...
Figure 3: Red (λmax = 633 nm), blue (λmax = 448 nm), green (λmax = 520 nm) and white (λmax = 620 nm) LEDs mou...
Figure 4: Overlap of absorption spectrum of methylene blue in acetonitrile and emission spectra of reasonably...
Figure 5: Emission spectra of different LEDs; red (λmax = 633 nm), blue (λmax = 448 nm), green (λmax = 520 nm...
Scheme 3: Slug flow conditions of two-phase gas-liquid mixtures. Photograph of a slug flow of a solution of m...
Figure 6: Photograph of the operating flow reactor, irradiated with white LEDs, filled with a solution of met...
Scheme 4: Schematic illustration of a reactor tube (length l, inner diameter d) and pressure gradient Δp acco...
Scheme 5: Reaction types of organic molecules with singlet oxygen.
Figure 7: Home-made flow reactor and peripheral devices for photochemical reactions at light/liquid/gas inter...
Scheme 6: Photooxygenation of N-methyl-1,2,3,6-tetrahydrophthalimide and reductive work-up to alcohol 3a.
Figure 8: Conversion vs methylene blue sensitizer concentration. Reactions at constant flow rates in acetonit...
Figure 9: Reaction progress at different residence times in flow and batch reactions. Flow: reactions at diff...
Scheme 7: Oxidation of N-methyl-1,2,3,6-tetrahydro-3-acetamidophthalimide and reductive work-up to alcohol 3b....
Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162
Graphical Abstract
Figure 1: The named transformations considered in this review.
Scheme 1: The Baeyer–Villiger oxidation.
Scheme 2: The general mechanism of the peracid-promoted Baeyer–Villiger oxidation.
Scheme 3: General mechanism of the Lewis acid-catalyzed Baeyer–Villiger rearrangement.
Scheme 4: The theoretically studied mechanism of the BV oxidation reaction promoted by H2O2 and the Lewis aci...
Scheme 5: Proton movements in the transition states of the Baeyer–Villiger oxidation.
Scheme 6: The dependence of the course of the Baeyer–Villiger oxidation on the type of O–O-bond cleavage in t...
Scheme 7: The acid-catalyzed Baeyer–Villiger oxidation of cyclic epoxy ketones 22.
Scheme 8: Oxidation of isophorone oxide 29.
Scheme 9: Synthesis of acyl phosphate 32 from acyl phosphonate 31.
Scheme 10: Synthesis of aflatoxin B2 (36).
Scheme 11: The Baeyer–Villiger rearrangement of ketones 37 to lactones 38.
Scheme 12: Synthesis of 3,4-dimethoxybenzoic acid (40) via Baeyer–Villiger oxidation.
Scheme 13: Oxone transforms α,β-unsaturated ketones 43 into vinyl acetates 44.
Scheme 14: The Baeyer–Villiger oxidation of ketones 45 using diaryl diselenide and hydrogen peroxide.
Scheme 15: Baeyer–Villiger oxidation of (E)-2-methylenecyclobutanones.
Scheme 16: Oxidation of β-ionone (56) by H2O2/(BnSe)2 with formation of (E)-2-(2,6,6-trimethylcyclohex-1-en-1-...
Scheme 17: The mechanism of oxidation of ketones 58a–f by hydrogen peroxide in the presence of arsonated polys...
Scheme 18: Oxidation of ketone (58b) by H2O2 to 6-methylcaprolactone (59b) catalyzed by Pt complex 66·BF4.
Scheme 19: Oxidation of ketones 67 with H2O2 in the presence of [(dppb}Pt(µ-OH)]22+.
Scheme 20: The mechanism of oxidation of ketones 67 in the presence of [(dppb}Pt(µ-OH)]22+ and H2O2.
Scheme 21: Oxidation of benzaldehydes 69 in the presence of the H2O2/MeReO3 system.
Scheme 22: Oxidation of acetophenones 72 in the presence of the H2O2/MeReO3 system.
Scheme 23: Baeyer–Villiger oxidation of 2-adamantanone (45c) in the presence of Sn-containing mesoporous silic...
Scheme 24: Aerobic Baeyer–Villiger oxidation of ketones 76 using metal-free carbon.
Scheme 25: A regioselective Baeyer-Villiger oxidation of functionalized cyclohexenones 78 into a dihydrooxepin...
Scheme 26: The oxidation of aldehydes and ketones 80 by H2O2 catalyzed by Co4HP2Mo15V3O62.
Scheme 27: The cleavage of ketones 82 with hydrogen peroxide in alkaline solution.
Scheme 28: Oxidation of ketones 85 to esters 86 with H2O2–urea in the presence of KHCO3.
Scheme 29: Mechanism of the asymmetric oxidation of cyclopentane-1,2-dione 87a with the Ti(OiPr)4/(+)DET/t-BuO...
Scheme 30: The oxidation of cis-4-tert-butyl-2-fluorocyclohexanone (93) with m-chloroperbenzoic acid.
Scheme 31: The mechanism of the asymmetric oxidation of 3-substituted cyclobutanone 96a in the presence of chi...
Scheme 32: Enantioselective Baeyer–Villiger oxidation of cyclic ketones 98.
Scheme 33: Regio- and enantioselective Baeyer–Villiger oxidation of cyclic ketones 101.
Scheme 34: The proposed mechanism of the Baeyer–Villiger oxidation of acetal 105f.
Scheme 35: Synthesis of hydroxy-10H-acridin-9-one 117 from tetramethoxyanthracene 114.
Scheme 36: The Baeyer–Villiger oxidation of the fully substituted pyrrole 120.
Scheme 37: The Criegee rearrangement.
Scheme 38: The mechanism of the Criegee reaction of a peracid with a tertiary alcohol 122.
Scheme 39: Criegee rearrangement of decaline ethylperoxoate 127 into ketal 128.
Scheme 40: The ionic cleavage of 2-methoxy-2-propyl perester 129.
Scheme 41: The Criegee rearrangement of α-methoxy hydroperoxide 136.
Scheme 42: Synthesis of enol esters and acetals via the Criegee rearrangement.
Scheme 43: Proposed mechanism of the transformation of 1-hydroperoxy-2-oxabicycloalkanones 147a–d.
Scheme 44: Transformation of 3-hydroxy-1,2-dioxolanes 151 into diketone derivatives 152.
Scheme 45: Criegee rearrangement of peroxide 153 with the mono-, di-, and tri-O-insertion.
Scheme 46: The sequential Criegee rearrangements of adamantanes 157a,b.
Scheme 47: Synthesis of diaryl carbonates 160a–d from triarylmethanols 159a–d through successive oxygen insert...
Scheme 48: The synthesis of sesquiterpenes 162 from ketone 161 with a Criegee rearrangement as one key step.
Scheme 49: Synthesis of trans-hydrindan derivatives 164, 165.
Scheme 50: The Hock rearrangement.
Scheme 51: The general scheme of the cumene process.
Scheme 52: The Hock rearrangement of aliphatic hydroperoxides.
Scheme 53: The mechanism of solvolysis of brosylates 174a–c and spiro cyclopropyl carbinols 175a–c in THF/H2O2....
Scheme 54: The fragmentation mechanism of hydroperoxy acetals 178 to esters 179.
Scheme 55: The acid-catalyzed rearrangement of phenylcyclopentyl hydroperoxide 181.
Scheme 56: The peroxidation of tertiary alcohols in the presence of a catalytic amount of acid.
Scheme 57: The acid-catalyzed reaction of bicyclic secondary alcohols 192 with hydrogen peroxide.
Scheme 58: The photooxidation of 5,6-disubstituted 3,4-dihydro-2H-pyrans 196.
Scheme 59: The oxidation of tertiary alcohols 200a–g, 203a,b, and 206.
Scheme 60: Transformation of functional peroxide 209 leading to 2,3-disubstitued furans 210 in one step.
Scheme 61: The synthesis of carbazoles 213 via peroxide rearrangement.
Scheme 62: The construction of C–N bonds using the Hock rearrangement.
Scheme 63: The synthesis of moiety 218 from 217 which is a structural motif in the antitumor–antibiotic of CC-...
Scheme 64: The in vivo oxidation steps of cholesterol (219) by singlet oxygen.
Scheme 65: The proposed mechanism of the rearrangement of cholesterol-5α-OOH 220.
Scheme 66: Photochemical route to artemisinin via Hock rearrangement of 223.
Scheme 67: The Kornblum–DeLaMare rearrangement.
Scheme 68: Kornblum–DeLaMare transformation of 1-phenylethyl tert-butyl peroxide (225).
Scheme 69: The synthesis 4-hydroxyenones 230 from peroxide 229.
Scheme 70: The Kornblum–DeLaMare rearrangement of peroxide 232.
Scheme 71: The reduction of peroxide 234.
Scheme 72: The Kornblum–DeLaMare rearrangement of endoperoxide 236.
Scheme 73: The rearrangement of peroxide 238 under Kornblum–DeLaMare conditions.
Scheme 74: The proposed mechanism of rearrangement of peroxide 238.
Scheme 75: The Kornblum–DeLaMare rearrangement of peroxides 242a,b.
Scheme 76: The base-catalyzed rearrangements of bicyclic endoperoxides having electron-withdrawing substituent...
Scheme 77: The base-catalyzed rearrangements of bicyclic endoperoxides 249a,b having electron-donating substit...
Scheme 78: The base-catalyzed rearrangements of bridge-head substituted bicyclic endoperoxides 251a,b.
Scheme 79: The Kornblum–DeLaMare rearrangement of hydroperoxide 253.
Scheme 80: Synthesis of β-hydroxy hydroperoxide 254 from endoperoxide 253.
Scheme 81: The amine-catalyzed rearrangement of bicyclic endoperoxide 263.
Scheme 82: The base-catalyzed rearrangement of meso-endoperoxide 268 into 269.
Scheme 83: The photooxidation of 271 and subsequent Kornblum–DeLaMare reaction.
Scheme 84: The Kornblum–DeLaMare rearrangement as one step in the oxidation reaction of enamines.
Scheme 85: The Kornblum–DeLaMare rearrangement of 3,5-dihydro-1,2-dioxenes 284, 1,2-dioxanes 286, and tert-but...
Scheme 86: The Kornblum–DeLaMare rearrangement of epoxy dioxanes 290a–d.
Scheme 87: Rearrangement of prostaglandin H2 292.
Scheme 88: The synthesis of epicoccin G (297).
Scheme 89: The Kornblum–DeLaMare rearrangement used in the synthesis of phomactin A.
Scheme 90: The Kornblum–DeLaMare rearrangement in the synthesis of 3H-quinazolin-4-one 303.
Scheme 91: The Kornblum–DeLaMare rearrangement in the synthesis of dolabriferol (308).
Scheme 92: Sequential transformation of 3-substituted 2-pyridones 309 into 3-hydroxypyridine-2,6-diones 311 in...
Scheme 93: The Kornblum–DeLaMare rearrangement of peroxide 312 into hydroxy enone 313.
Scheme 94: The Kornblum–DeLaMare rearrangement in the synthesis of polyfunctionalized carbonyl compounds 317.
Scheme 95: The Kornblum–DeLaMare rearrangement in the synthesis of (Z)-β-perfluoroalkylenaminones 320.
Scheme 96: The Kornblum–DeLaMare rearrangement in the synthesis of γ-ketoester 322.
Scheme 97: The Kornblum–DeLaMare rearrangement in the synthesis of diterpenoids 326 and 328.
Scheme 98: The synthesis of natural products hainanolidol (331) and harringtonolide (332) from peroxide 329.
Scheme 99: The synthesis of trans-fused butyrolactones 339 and 340.
Scheme 100: The synthesis of leucosceptroid C (343) and leucosceptroid P (344) via the Kornblum–DeLaMare rearra...
Scheme 101: The Dakin oxidation of arylaldehydes or acetophenones.
Scheme 102: The mechanism of the Dakin oxidation.
Scheme 103: A solvent-free Dakin reaction of aromatic aldehydes 356.
Scheme 104: The organocatalytic Dakin oxidation of electron-rich arylaldehydes 358.
Scheme 105: The Dakin oxidation of electron-rich arylaldehydes 361.
Scheme 106: The Dakin oxidation of arylaldehydes 358 in water extract of banana (WEB).
Scheme 107: A one-pot approach towards indolo[2,1-b]quinazolines 364 from indole-3-carbaldehydes 363 through th...
Scheme 108: The synthesis of phenols 367a–c from benzaldehydes 366a-c via acid-catalyzed Dakin oxidation.
Scheme 109: Possible transformation paths of the highly polarized boric acid coordinated H2O2–aldehyde adduct 3...
Scheme 110: The Elbs oxidation of phenols 375 to hydroquinones.
Scheme 111: The mechanism of the Elbs persulfate oxidation of phenols 375 affording p-hydroquinones 376.
Scheme 112: Oxidation of 2-pyridones 380 under Elbs persulfate oxidation conditions.
Scheme 113: Synthesis of 3-hydroxy-4-pyridone (384) via an Elbs oxidation of 4-pyridone (382).
Scheme 114: The Schenck rearrangement.
Scheme 115: The Smith rearrangement.
Scheme 116: Three main pathways of the Schenck rearrangement.
Scheme 117: The isomerization of hydroperoxides 388 and 389.
Scheme 118: Trapping of dioxacyclopentyl radical 392 by oxygen.
Scheme 119: The hypothetical mechanism of the Schenck rearrangement of peroxide 394.
Scheme 120: The autoxidation of oleic acid (397) with the use of labeled isotope 18O2.
Scheme 121: The rearrangement of 18O-labeled hydroperoxide 400 under an atmosphere of 16O2.
Scheme 122: The rearrangement of the oleate-derived allylic hydroperoxides (S)-421 and (R)-425.
Scheme 123: Mechanisms of Schenck and Smith rearrangements.
Scheme 124: The rearrangement and cyclization of 433.
Scheme 125: The Wieland rearrangement.
Scheme 126: The rearrangement of bis(triphenylsilyl) 439 or bis(triphenylgermyl) 441 peroxides.
Scheme 127: The oxidative transformation of cyclic ketones.
Scheme 128: The hydroxylation of cyclohexene (447) in the presence of tungstic acid.
Scheme 129: The oxidation of cyclohexene (447) under the action of hydrogen peroxide.
Scheme 130: The reaction of butenylacetylacetone 455 with hydrogen peroxide.
Scheme 131: The oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 132: The proposed mechanism for the oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 133: The rearrangement of ozonides.
Scheme 134: The acid-catalyzed oxidative rearrangement of malondialdehydes 462 under the action of H2O2.
Scheme 135: Pathways of the Lewis acid-catalyzed cleavage of dialkyl peroxides 465 and ozonides 466.
Scheme 136: The mechanism of the transformation of (tert-butyldioxy)cyclohexanedienones 472.
Scheme 137: The synthesis of Vitamin K3 from 472a.
Scheme 138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Scheme 139: The rearrangement of hydroperoxide 485 to form diketone 486.
Scheme 140: The base-catalyzed rearrangement of cyclic peroxides 488a–g.
Scheme 141: Synthesis of chiral epoxides and aldols from peroxy hemiketals 491.
Scheme 142: The multistep transformation of (R)-carvone (494) to endoperoxides 496a–e.
Scheme 143: The decomposition of anthracene endoperoxide 499.
Scheme 144: Synthesis of esters 503 from aldehydes 501 via rearrangement of peroxides 502.
Scheme 145: Two possible paths for the base-promoted decomposition of α-azidoperoxides 502.
Scheme 146: The Story decomposition of cyclic diperoxide 506a.
Scheme 147: The Story decomposition of cyclic triperoxide 506b.
Scheme 148: The thermal rearrangement of endoperoxides A into diepoxides B.
Scheme 149: The transformation of peroxide 510 in the synthesis of stemolide (511).
Scheme 150: The possible mechanism of the rearrangement of endoperoxide 261g.
Scheme 151: The photooxidation of indene 517.
Scheme 152: The isomerization of ascaridole (523).
Scheme 153: The isomerization of peroxide 525.
Scheme 154: The thermal transformation of endoperoxide 355.
Scheme 155: The photooxidation of cyclopentadiene (529) at a temperature higher than 0 °C.
Scheme 156: The thermal rearrangement of endoperoxides 538a,b.
Scheme 157: The transformation of peroxides 541.
Scheme 158: The thermal rearrangements of strained cyclic peroxides.
Scheme 159: The thermal rearrangement of diacyl peroxide 551 in the synthesis of C4-epi-lomaiviticin B core 553....
Scheme 160: The 1O2 oxidation of tryptophan (554) and rearrangement of dioxetane intermediate 555.
Scheme 161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Scheme 162: The proposed mechanism of the Fe(II)-promoted rearrangement of 557a–c.
Scheme 163: The reaction of dioxolane 563 with Fe(II) sulfate.
Scheme 164: Fe(II)-promoted rearrangement of 1,2-dioxane 565.
Scheme 165: Fe(II) cysteinate-promoted rearrangement of 1,2-dioxolane 568.
Scheme 166: The transformation of 1,2-dioxanes 572a–c under the action of FeCl2.
Scheme 167: Fe(II) cysteinate-promoted transformation of tetraoxane 574.
Scheme 168: The CoTPP-catalyzed transformation of bicyclic endoperoxides 600a–d.
Scheme 169: The CoTPP-catalyzed transformation of epoxy-1,2-dioxanes.
Scheme 170: The Ru(II)-catalyzed reactions of 1,4-endoperoxide 261g.
Scheme 171: The Ru(II)-catalyzed transformation as a key step in the synthesis of elyiapyrone A (610) from 1,4-...
Scheme 172: Peroxides with antimalarial activity.
Scheme 173: The interaction of iron ions with artemisinin (616).
Scheme 174: The interaction of FeCl2 with 1,2-dioxanes 623, 624.
Scheme 175: The mechanism of reaction 623 and 624 with Fe(II)Cl2.
Scheme 176: The reaction of bicyclic natural endoperoxides G3-factors 631–633 with FeSO4.
Scheme 177: The transformation of terpene cardamom peroxide 639.
Scheme 178: The different ways of the cleavage of tetraoxane 643.
Scheme 179: The LC–MS analysis of interaction of tetraoxane 646 with iron(II)heme 647.
Scheme 180: The rearrangement of 3,6-epidioxy-1,10-bisaboladiene (EDBD, 649).
Scheme 181: Easily oxidized substrates.
Scheme 182: Biopathway of synthesis of prostaglandins.
Scheme 183: The reduction and rearrangements of isoprostanes.
Scheme 184: The partial mechanism for linoleate 658 oxidation.
Scheme 185: The transformation of lipid hydroperoxide.
Scheme 186: The acid-catalyzed cleavage of the product from free-radical oxidation of cholesterol (667).
Scheme 187: Two pathways of catechols oxidation.
Scheme 188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme...
Scheme 189: Carotinoides 679 cleavage by carotenoid cleavage dioxygenases.
Beilstein J. Org. Chem. 2016, 12, 1196–1202, doi:10.3762/bjoc.12.115
Graphical Abstract
Figure 1: Chemical structure of the photosensitizing chromophores benzophenone (BZP) and 2-benzoylthiophene (...
Figure 2: Chemical structure of tiaprofenic acid (TPA) and suprofen (SP).
Figure 3: Chemical structures of dyads 1–3.
Scheme 1: Formation of products 4 and 5 upon photolysis of dyads 1 and 2.
Figure 4: Diagnostic NOE interactions in compounds 4 and 5.
Figure 5: Decrease of the absorbance at 290 nm upon irradiation in CH2Cl2 under N2 for 1 (red circles), 2 (bl...
Figure 6: Transient absorption spectra for dyad 1 in CH2Cl2 1 μs after laser pulse (λexc = 355 nm). Inset: No...
Scheme 2: Photoreaction pathways generating biradical and singlet oxygen species of a sensitizer (S), like SP...
Figure 7: Time-resolved experiments at 1270 nm upon excitation at 308 nm of aerated CH2Cl2 solutions of 1–3, ...
Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69
Graphical Abstract
Scheme 1: The formation of a 1:1 complex and a 2:1 supramolecular nano-capsule complex from bowl-shaped “cavi...
Scheme 2: Abbreviated synthesis of 7-amino-2-phenyl-6-azaindolizine.
Figure 1: My two favorite compounds for my Ph.D. dissertation, “The Synthesis and Structural Examination of 3...
Scheme 3: An inspiring chlorination from the group of Ronald Breslow.
Scheme 4: The carceplex reaction.
Figure 2: Schematic of a cavitein.
Figure 3: General structure of zinc-TPA complexes.
Scheme 5: Stereoselective bridging of a resorcinarene with benzal halides.
Scheme 6: An eight-fold Ullman ether “weaving” reaction.
Scheme 7: Directed ortho-metallation of the deep-cavity cavitands, showing the mono-endo substituted to tetra-...
Scheme 8: Macrocycle synthesis via resorcinarene covalent templates.
Figure 4: Tris-pyridyl hosts.
Figure 5: (Center) Chemical structure of the octa-acid host. (Left and right) Respective space-filling repres...
Figure 6: Cartoons of the 2:1 host–guest complexes of estradiol (left) and cholesterol (right).
Figure 7: Representative guests for the capsular complexes formed by octa-acid (stoichiometry shown in parent...
Figure 8: A dendrimer-coated cavitand.
Figure 9: Selective oxidation of olefins by singlet oxygen.
Figure 10: a) Preferred packing motifs of methyl, pentyl and octyl guests. b) Product distribution observed fo...
Figure 11: Schematic of the competition of two esters for the capsule formed by octa-acid. The ester that bind...
Figure 12: Schematic of the inter-phase separation of propane and butane; the latter binds more strongly to th...
Figure 13: Structure of tetra-endo-methyl octa-acid (TEMOA).
Figure 14: Assembly properties of TEMOA.
Figure 15: How salts influence the association constant (Ka) for the binding of ClO4– to octa-acid (Figure 4). The ind...
Beilstein J. Org. Chem. 2015, 11, 1246–1258, doi:10.3762/bjoc.11.139
Graphical Abstract
Scheme 1: The polyenes 2 stabilized by terminal tert-butyl substituents.
Scheme 2: The catalytic hydrogenation of diene 3.
Figure 1: The structure of compound 4 in the crystal. Ellipsoids correspond to 30% probability levels.
Scheme 3: The catalytic hydrogenation of triene 7.
Scheme 4: Addition of bromine to model dienes.
Scheme 5: Bromine addition to diene 3 and triene 7.
Scheme 6: Bromine addition to the higher oligoenes 19–22.
Figure 2: (a) The structure of compound 24 in the crystal. Ellipsoids correspond to 50% probability levels. (...
Figure 3: The structure of compound 25 in the crystal. This was a structure of poor quality and served only t...
Scheme 7: Epoxidation of triene 7 with MCPBA and DMDO.
Scheme 8: Epoxidation of tetraene 19 with MCPBA and DMDO.
Scheme 9: Diels–Alder addition of PTAD (36) to triene 7 and tetraene 19.
Figure 4: The structure of compound 37 in the crystal. Only one of two independent molecules is shown. Ellips...
Scheme 10: Diels-Alder addition of oligoenes 20 and 21 with PTAD (36).
Scheme 11: Addition of excess PTAD (36) to hexaene 21 and heptaene 22.
Scheme 12: TCNE addition to oligoolefins: from tetraene 19 to nonaene 42.
Figure 5: The structure of compound 43 in the crystal. Only one of two independent molecules is shown. Ellips...
Scheme 13: Photochemical experiments with tetraene 19.
Figure 6: The structure of compound 52 in the crystal. Ellipsoids correspond to 50% probability levels.
Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118
Graphical Abstract
Figure 1: Chemical structures of the target dyes 1 and 2.
Scheme 1: Synthetic routes to the target dyes 1 (top) and 2 (bottom).
Figure 2: Cyclic voltammograms of 1 (blue line), 2 (red line) and 6 (black line) in CH2Cl2 (0.1 M Bu4NPF6; Pt...
Figure 3: Electronic absorption spectra of 1 (blue line) and 2 (red line) in CH2Cl2 solutions.
Figure 4: Photovoltaic performance of the two sensitizers. Photocurrent density (J) as a function of voltage ...
Beilstein J. Org. Chem. 2015, 11, 668–674, doi:10.3762/bjoc.11.75
Graphical Abstract
Figure 1: Cartoon of a divalent carbohydrate-scaffolded molecular architecture that allows control of the fle...
Scheme 1: Synthesis of carbohydrate-scaffolded dimeric thymine 7 and intramolecular photocycloaddition. The i...
Figure 2: 1H NMR spectra (all in D2O, 500 MHz) of mannoside 7 (A) and of the irradiation product (8) after 3 ...
Scheme 2: Synthesis of carbohydrate-scaffolded dimeric glycothymine 13 and intramolecular photocycloaddition....
Figure 3: 1H NMR spectra (all in D2O, 500 MHz) of mannoside 13 (A) and of the irradiation product (14) after ...
Beilstein J. Org. Chem. 2014, 10, 2556–2565, doi:10.3762/bjoc.10.267
Graphical Abstract
Figure 1: CO2 reduction to methanol in water promoted by FateDH, FaldDH and ADH where three consecutive 2e− s...
Figure 2: Transformed diffuse reflectance spectra of photocatalysts used in the present study.
Figure 3: a) Photoregeneration of 1,4-NADH using water as an electron donor: after 6 hours of irradiation of ...
Figure 4: 1H NMR spectra recorded at t = 0, after 2 and 6 h of irradiation in water. The selected range, 2–3 ...
Figure 5: 1H NMR spectrum of a standard 1,4-NADH (red line), and of 1,4-NADH formed from NAD+ upon photocatal...
Figure 6: Photocurrent generated at the [CrF5(H2O)]2−@TiO2 electrode as a function of the wavelength of the i...
Figure 7: Expected role of the rhodium complex as an electron mediator.
Figure 8: UV–vis absorption spectra of an aqueous solution of [Cp*Rh(bpy)(H2O)]2+. Continuous black line: spe...
Figure 9: Spectral changes of the [Cp*Rh(bpy)(H2O)]2+ solution as a function of the applied potential (left)....
Figure 10: Photoreduction of NAD+ as a function of concentration of glycerol (black line) and [Cp*Rh(bpy)H2O]Cl...
Figure 11: The electron flow in the photocatalytic system of NAD+ reduction composed of the photosensitized TiO...
Figure 12: Beads produced from Ca-alginate and TEOS containing co-encapsulated FateDH, FaldDH and ADH.
Figure 13: Assembled photocatalytic/enzymatic system for reduction of CO2 to CH3OH.
Beilstein J. Org. Chem. 2014, 10, 2448–2452, doi:10.3762/bjoc.10.255
Graphical Abstract
Figure 1: Structures of compounds 1–3.
Scheme 1: Hypothetical one-pot synthesis of compound 4a and/or 4b.
Figure 2: Structure of compound 6 determined by single crystal X-ray diffractometry.
Scheme 2: Evaluation of the substrate scope using RB as oxygen (1O2) sensitizer “on water”.
Scheme 3: Evaluation of the oxidative coupling in the absence of RB, on water.
Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212
Graphical Abstract
Figure 1: Common photoremovable protecting groups (PPGs) for phosphates depicted as diethyl phosphate (DEP) e...
Scheme 1: Synthesis of 2,6-HNA DEP (10), 1,4-HNA DEP (14a), and 1,4-MNA DEP (14b) DEP esters. Reagents and co...
Scheme 2: Synthesis of diethyl 8-(benzyloxy)quinolin-5-yl)-2-oxoethyl phosphate (5,8-BQA DEP, 24). Reagents a...
Figure 2: A. UV–vis spectrum of 14a (1,4-HNA DEP) in 1% aq MeCN. B. Fluorescence emission/excitation spectra ...
Scheme 3: Photolysis of 1,4-HNA and 1,4-MNA diethyl phosphates 14a and 14b in aq MeOH.
Scheme 4: The photo-Favorskii rearrangement of 14a.
Scheme 5: Photolysis of 2,6-HNA DEP (10) in 1% aq MeCN.
Scheme 6: Photolysis of 5,8-BQA diethyl phosphate (24).
Figure 3: Naphthyl and quinolin-5-yl caged phosphate esters 10, 14, 24 and 27 (acetate ester).
Figure 4: Previously studied caged diethyl phosphate PPGs possessing aromatic (benzyl, phenacyl, and naphthyl...
Scheme 7: Photo-Favorskii mechanism based on pHP DEP 4a photochemistry as applied to 1,4-HNA DEP (14a).
Scheme 8: Photodehydration and substitution of 5-(1-hydroxyethyl)-1-naphthol 34 [19].
Scheme 9: Putative rearrangement intermediates for 1,5- and 2,6- HNA chromophores.
Beilstein J. Org. Chem. 2014, 10, 1143–1150, doi:10.3762/bjoc.10.114
Graphical Abstract
Scheme 1: Photohydroxymethylation of carbonyl compounds and imines.
Scheme 2: Model process: photocatalyzed acetophenone/methanol reaction.
Scheme 3: Photocatalyzed acetophenone/methanol reaction: types I–III.
Scheme 4: Photohydroxymethylation and subsequent lactonization of keto esters.
Scheme 5: Model reaction for heterogeneous and dye-sensitized catalysis.
Scheme 6: Product forming routes I to III for photoredox catalysis of methanol/carbonyl compounds.
Scheme 7: Photoredox initiated steps on semiconductor particle surfaces, CB, VB = conduction and valence band....
Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83
Graphical Abstract
Scheme 1: Examples of photoinitiating systems.
Figure 1: Previously reported PIC (based on metal complexes) [45-52].
Figure 2: Previously reported PIC (metal free organic molecules) [54,55].
Scheme 2: Reaction mechanisms for the three-component system PIC/eA/E-Z.
Scheme 3: Reaction mechanisms for the two-component system PIC/eA.
Scheme 4: Reaction mechanisms for the system PIC/eA/add.
Scheme 5: Reaction mechanisms for the system PIC/eD/B-Y.
Figure 3: Typical oxidation and reduction agents used through the photoredox catalysis approach in polymeriza...
Figure 4: Typical monomers that can be polymerized through a photoredox catalysis approach.
Scheme 6: Reaction mechanisms for the system Ru(bpy)32+/Ph2I+/R3SiH.
Scheme 7: Reaction mechanisms for the Ru(ligand)32+/Ph3S+/R3SiH system.
Scheme 8: Reaction mechanisms for the Ru(ligand)32+/Ph2I+/NVK system upon visible lights.
Scheme 9: Reaction mechanisms for the violanthrone/Ph2I+/TTMSS (R3SiH) system upon red lights.
Scheme 10: Reaction mechanisms for the Tr-AD/R-Br/MDEA system upon visible lights.
Scheme 11: The photoredox catalysis for controlled polymerization reactions.
Scheme 12: Reaction mechanisms for the Ru(ligand)32+/MDEA/R-Br system upon visible lights.
Scheme 13: Reaction mechanisms for the Violanthrone/Ru(ligand)32+/Ph2I+/R3SiH system upon visible lights.
Scheme 14: Reaction mechanisms for the MK/amine/triazine system upon visible lights.
Figure 5: The new proposed PIC (Ir(piq)2(tmd)).
Figure 6: UV–visible light absorption spectra for Ir(piq)2(tmd) (2) and Ir(ppy)3 (1); solvent: acetonitrile.
Figure 7: (A) cyclic voltamogramm for Ir(piq)2(tmd) in acetonitrile; (B) absorption (a) and luminescence (b) ...
Figure 8: Photolysis of a Ir(piq)2(tmd)/Ph2I+ solution ([Ph2I+] = 0.023 M, in acetonitrile) upon a halogen la...
Figure 9: ESR spin-trapping spectra for the irradiation of a Ir(piq)2(tmd)/Ph2I+ solution in the presence of ...
Figure 10: (A) Photopolymerization profile of EPOX; photoinitiating system: Ir(piq)2(tmd)/Ph2I+/NVK (1%/2%/3%)...
Figure 11: (A) Photopolymerization profile of TMPTA; initiating systems: (1) Ir(piq)2(tmd)/MDEA (1%/2%) and (2...
Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6
Graphical Abstract
Figure 1: Five and six-membered cyclic peroxides.
Figure 2: Artemisinin and semi-synthetic derivatives.
Scheme 1: Synthesis of 3-hydroxy-1,2-dioxolanes 3a–c.
Scheme 2: Synthesis of dioxolane 6.
Scheme 3: Photooxygenation of oxazolidines 7a–d with formation of spiro-fused oxazolidine-containing dioxolan...
Scheme 4: Oxidation of cyclopropanes 10a–e and 11a–e with preparation of 1,2-dioxolanes 12a–e.
Scheme 5: VO(acac)2-catalyzed oxidation of silylated bicycloalkanols 13a–c.
Scheme 6: Mn(II)-catalyzed oxidation of cyclopropanols 15a–g.
Scheme 7: Oxidation of aminocyclopropanes 20a–c.
Scheme 8: Synthesis of aminodioxolanes 24.
Figure 3: Trifluoromethyl-containing dioxolane 25.
Scheme 9: Synthesis of 1,2-dioxolanes 27a–e by the oxidation of cyclopropanes 26a–e.
Scheme 10: Photoinduced oxidation of methylenecyclopropanes 28.
Scheme 11: Irradiation-mediated oxidation.
Scheme 12: Application of diazene 34 for dioxolane synthesis.
Scheme 13: Mn(OAc)3-catalyzed cooxidation of arylacetylenes 37a–h and acetylacetone with atmospheric oxygen.
Scheme 14: Peroxidation of (2-vinylcyclopropyl)benzene (40).
Scheme 15: Peroxidation of 1,4-dienes 43a,b.
Scheme 16: Peroxidation of 1,5-dienes 46.
Scheme 17: Peroxidation of oxetanes 53a,b.
Scheme 18: Peroxidation of 1,6-diene 56.
Scheme 19: Synthesis of 3-alkoxy-1,2-dioxolanes 62a,b.
Scheme 20: Synthesis of spiro-bis(1,2-dioxolane) 66.
Scheme 21: Synthesis of dispiro-1,2-dioxolanes 68, 70, 71.
Scheme 22: Synthesis of spirohydroperoxydioxolanes 75a,b.
Scheme 23: Synthesis of spirohydroperoxydioxolane 77 and dihydroperoxydioxolane 79.
Scheme 24: Ozonolysis of azepino[4,5-b]indole 80.
Scheme 25: SnCl4-mediated fragmentation of ozonides 84a–l in the presence of allyltrimethylsilane.
Scheme 26: SnCl4-mediated fragmentation of bicyclic ozonide 84m in the presence of allyltrimethylsilane.
Scheme 27: MCl4-mediated fragmentation of alkoxyhydroperoxides 96 in the presence of allyltrimethylsilane.
Scheme 28: SnCl4-catalyzed reaction of monotriethylsilylperoxyacetal 108 with alkene 109.
Scheme 29: SnCl4-catalyzed reaction of triethylsilylperoxyacetals 111 with alkenes.
Scheme 30: Desilylation of tert-butyldimethylsilylperoxy ketones 131a,b followed by cyclization.
Scheme 31: Deprotection of peroxide 133 followed by cyclization.
Scheme 32: Asymmetric peroxidation of methyl vinyl ketones 137a–e.
Scheme 33: Et2NH-catalyzed intramolecular cyclization.
Scheme 34: Synthesis of oxodioxolanes 143a–j.
Scheme 35: Haloperoxidation accompanied by intramolecular ring closure.
Scheme 36: Oxidation of triterpenes 149a–d with Na2Cr2O7/N-hydroxysuccinimide.
Scheme 37: Curtius and Wolff rearrangements to form 1,2-dioxolane ring-retaining products.
Scheme 38: Oxidative desilylation of peroxide 124.
Scheme 39: Synthesis of dioxolane 158, a compound containing the aminoquinoline antimalarial pharmacophore.
Scheme 40: Diastereomers of plakinic acid A, 162a and 162b.
Scheme 41: Ozonolysis of alkenes.
Scheme 42: Cross-ozonolysis of alkenes 166 with carbonyl compounds.
Scheme 43: Ozonolysis of the bicyclic cyclohexenone 168.
Scheme 44: Cross-ozonolysis of enol ethers 172a,b with cyclohexanone.
Scheme 45: Griesbaum co-ozonolysis.
Scheme 46: Reactions of aryloxiranes 177a,b with oxygen.
Scheme 47: Intramolecular formation of 1,2,4-trioxolane 180.
Scheme 48: Formation of 1,2,4-trioxolane 180 by the reaction of 1,5-ketoacetal 181 with H2O2.
Scheme 49: 1,2,4-Trioxolane 186 with tetrazole fragment.
Scheme 50: 1,2,4-Trioxolane 188 with a pyridine fragment.
Scheme 51: 1,2,4-Trioxolane 189 with pyrimidine fragment.
Scheme 52: Synthesis of aminoquinoline-containing 1,2,4-trioxalane 191.
Scheme 53: Synthesis of arterolane.
Scheme 54: Oxidation of diarylheptadienes 197a–c with singlet oxygen.
Scheme 55: Synthesis of hexacyclinol peroxide 200.
Scheme 56: Oxidation of enone 201 and enenitrile 203 with singlet oxygen.
Scheme 57: Synthesis of 1,2-dioxanes 207 by oxidative coupling of carbonyl compounds 206 and alkenes 205.
Scheme 58: 1,2-Dioxanes 209 synthesis by co-oxidation of 1,5-dienes 208 and thiols.
Scheme 59: Synthesis of bicyclic 1,2-dioxanes 212 with aryl substituents.
Scheme 60: Isayama–Mukaiyama peroxysilylation of 1,5-dienes 213 followed by desilylation under acidic conditio...
Scheme 61: Synthesis of bicycle 218 with an 1,2-dioxane ring.
Scheme 62: Intramolecular cyclization with an oxirane-ring opening.
Scheme 63: Inramolecular cyclization with the oxetane-ring opening.
Scheme 64: Intramolecular cyclization with the attack on a keto group.
Scheme 65: Peroxidation of the carbonyl group in unsaturated ketones 228 followed by cyclization of hydroperox...
Scheme 66: CsOH and Et2NH-catalyzed cyclization.
Scheme 67: Preparation of peroxyplakoric acid methyl ethers A and D.
Scheme 68: Hg(OAc)2 in 1,2-dioxane synthesis.
Scheme 69: Reaction of 1,4-diketones 242 with hydrogen peroxide.
Scheme 70: Inramolecular cyclization with oxetane-ring opening.
Scheme 71: Inramolecular cyclization with MsO fragment substitution.
Scheme 72: Synthesis of 1,2-dioxane 255a, a structurally similar compound to natural peroxyplakoric acids.
Scheme 73: Synthesis of 1,2-dioxanes based on the intramolecular cyclization of hydroperoxides containing C=C ...
Scheme 74: Use of BCIH in the intramolecular cyclization.
Scheme 75: Palladium-catalyzed cyclization of δ-unsaturated hydroperoxides 271a–e.
Scheme 76: Intramolecular cyclization of unsaturated peroxyacetals 273a–d.
Scheme 77: Allyltrimethylsilane in the synthesis of 1,2-dioxanes 276a–d.
Scheme 78: Intramolecular cyclization using the electrophilic center of the peroxycarbenium ion 279.
Scheme 79: Synthesis of bicyclic 1,2-dioxanes.
Scheme 80: Preparation of 1,2-dioxane 286.
Scheme 81: Di(tert-butyl)peroxalate-initiated radical cyclization of unsaturated hydroperoxide 287.
Scheme 82: Oxidation of 1,4-betaines 291a–d.
Scheme 83: Synthesis of aminoquinoline-containing 1,2-dioxane 294.
Scheme 84: Synthesis of the sulfonyl-containing 1,2-dioxane.
Scheme 85: Synthesis of the amido-containing 1,2-dioxane 301.
Scheme 86: Reaction of singlet oxygen with the 1,3-diene system 302.
Scheme 87: Synthesis of (+)-premnalane А and 8-epi-premnalane A.
Scheme 88: Synthesis of the diazo group containing 1,2-dioxenes 309a–e.
Figure 4: Plakortolide Е.
Scheme 89: Synthesis of 6-epiplakortolide Е.
Scheme 90: Application of Bu3SnH for the preparation of tetrahydrofuran-containing bicyclic peroxides 318a,b.
Scheme 91: Application of Bu3SnH for the preparation of lactone-containing bicyclic peroxides 320a–f.
Scheme 92: Dihydroxylation of the double bond in the 1,2-dioxene ring 321 with OsO4.
Scheme 93: Epoxidation of 1,2-dioxenes 324.
Scheme 94: Cyclopropanation of the double bond in endoperoxides 327.
Scheme 95: Preparation of pyridazine-containing bicyclic endoperoxides 334a–c.
Scheme 96: Synthesis of 1,2,4-trioxanes 337 by the hydroperoxidation of unsaturated alcohols 335 with 1O2 and ...
Scheme 97: Synthesis of sulfur-containing 1,2,4-trioxanes 339.
Scheme 98: BF3·Et2O-catalyzed synthesis of the 1,2,4-trioxanes 342a–g.
Scheme 99: Photooxidation of enol ethers or vinyl sulfides 343.
Scheme 100: Synthesis of tricyclic peroxide 346.
Scheme 101: Reaction of endoperoxides 348a,b derived from cyclohexadienes 347a,b with 1,4-cyclohexanedione.
Scheme 102: [4 + 2]-Cycloaddition of singlet oxygen to 2Н-pyrans 350.
Scheme 103: Synthesis of 1,2,4-trioxanes 354 using peroxysilylation stage.
Scheme 104: Epoxide-ring opening in 355 with H2O2 followed by the condensation of hydroxy hydroperoxides 356 wi...
Scheme 105: Peroxidation of unsaturated ketones 358 with the H2O2/CF3COOH/H2SO4 system.
Scheme 106: Synthesis of 1,2,4-trioxanes 362 through Et2NH-catalyzed intramolecular cyclization.
Scheme 107: Reduction of the double bond in tricyclic peroxides 363.
Scheme 108: Horner–Wadsworth–Emmons reaction in the presence of peroxide group.
Scheme 109: Reduction of ester group by LiBH4 in the presence of 1,2,4-trioxane moiety.
Scheme 110: Reductive amination of keto-containing 1,2,4-trioxane 370.
Scheme 111: Reductive amination of keto-containing 1,2,4-trioxane and a Fe-containing moiety.
Scheme 112: Acid-catalyzed reactions of Н2О2 with ketones and aldehydes 374.
Scheme 113: Cyclocondensation of carbonyl compounds 376a–d using Me3SiOOSiMe3/CF3SO3SiMe3.
Scheme 114: Peroxidation of 4-methylcyclohexanone (378).
Scheme 115: Synthesis of symmetrical tetraoxanes 382a,b from aldehydes 381a,b.
Scheme 116: Synthesis of unsymmetrical tetraoxanes using of MeReO3.
Scheme 117: Synthesis of symmetrical tetraoxanes using of MeReO3.
Scheme 118: Synthesis of symmetrical tetraoxanes using of MeReO3.
Scheme 119: MeReO3 in the synthesis of symmetrical tetraoxanes with the use of aldehydes.
Scheme 120: Preparation of unsymmmetrical 1,2,4,5-tetraoxanes with high antimalarial activity.
Scheme 121: Re2O7-Catalyzed synthesis of tetraoxanes 398.
Scheme 122: H2SO4-Catalyzed synthesis of steroidal tetraoxanes 401.
Scheme 123: HBF4-Catalyzed condensation of bishydroperoxide 402 with 1,4-cyclohexanedione.
Scheme 124: BF3·Et2O-Catalyzed reaction of gem-bishydroperoxides 404 with enol ethers 405 and acetals 406.
Scheme 125: HBF4-Catalyzed cyclocondensation of bishydroperoxide 410 with ketones.
Scheme 126: Synthesis of symmetrical and unsymmetrical tetraoxanes 413 from benzaldehydes 412.
Scheme 127: Synthesis of bridged 1,2,4,5-tetraoxanes 415a–l from β-diketones 414a–l and H2O2.
Scheme 128: Dimerization of zwitterions 417.
Scheme 129: Ozonolysis of verbenone 419.
Scheme 130: Ozonolysis of O-methyl oxime 424.
Scheme 131: Peroxidation of 1,1,1-trifluorododecan-2-one 426 with oxone.
Scheme 132: Intramolecular cyclization of dialdehyde 428 with H2O2.
Scheme 133: Tetraoxanes 433–435 as by-products in peroxidation of ketals 430–432.
Scheme 134: Transformation of triperoxide 436 in diperoxide 437.
Scheme 135: Preparation and structural modifications of tetraoxanes.
Scheme 136: Structural modifications of steroidal tetraoxanes.
Scheme 137: Synthesis of 1,2,4,5-tetraoxane 454 containing the fluorescent moiety.
Scheme 138: Synthesis of tetraoxane 458 (RKA182).
Beilstein J. Org. Chem. 2013, 9, 1977–2001, doi:10.3762/bjoc.9.234
Graphical Abstract
Scheme 1: Amine radical cations’ mode of reactivity.
Scheme 2: Reductive quenching of photoexcited Ru complexes by Et3N.
Scheme 3: Photoredox aza-Henry reaction.
Scheme 4: Formation of iminium ions using BrCCl3 as stoichiometric oxidant.
Scheme 5: Oxidative functionalization of N-aryltetrahydroisoquinolines using Eosin Y.
Scheme 6: Synthetic and mechanistic studies of Eosin Y-catalyzed aza-Henry reaction.
Scheme 7: Oxidative functionalization of N-aryltetrahydroisoquinolines using RB and GO.
Scheme 8: Merging Ru-based photoredox catalysis and Lewis base catalysis for the Mannich reaction.
Scheme 9: Merging Au-based photoredox catalysis and Lewis base catalysis for the Mannich reaction.
Scheme 10: Merging Ru-based photoredox catalysis and Cu-catalyzed alkynylation reaction.
Scheme 11: Merging Ru-based photoredox catalysis and NHC catalysis.
Scheme 12: 1,3-Dipolar cycloaddition of photogenically formed azomethine ylides.
Scheme 13: Plausible mechanism for photoredox 1,3-dipolar cycloaddition.
Scheme 14: Photoredox-catalyzed cascade reaction for the synthesis of fused isoxazolidines.
Scheme 15: Plausible mechanism for the photoredox-catalyzed cascade reaction.
Scheme 16: Photoredox-catalyzed α-arylation of glycine derivatives.
Scheme 17: Photoredox-catalyzed α-arylation of amides.
Scheme 18: Intramolecular interception of iminium ions by sulfonamides.
Scheme 19: Intramolecular interception of iminium ions by alcohols and sulfonamides.
Scheme 20: Intermolecular interception of iminium ions by phosphites.
Scheme 21: Photoredox-catalyzed oxidative phosphonylation by Eosin Y.
Scheme 22: Conjugated addition of α-amino radicals to Michael acceptors.
Scheme 23: Conjugated addition of α-amino radicals to Michael acceptors assisted by a Brønsted acid.
Scheme 24: Conjugated addition of α-amino radicals derived from anilines to Michael acceptors.
Scheme 25: Oxygen switch between two pathways involving α-amino radicals.
Scheme 26: Interception of α-amino radicals by azodicarboxylates.
Scheme 27: α-Arylation of amines.
Scheme 28: Plausible mechanism for α-arylation of amines.
Scheme 29: Photoinduced C–C bond cleavage of tertiary amines.
Scheme 30: Photoredox cleavage of C–C bonds of 1,2-diamines.
Scheme 31: Proposed mechanism photoredox cleavage of C–C bonds.
Scheme 32: Intermolecular [3 + 2] annulation of cyclopropylamines with olefins.
Scheme 33: Proposed mechanism for intermolecular [3 + 2] annulation.
Scheme 34: Photoinduced clevage of N–N bonds of aromatic hydrazines and hydrazides.
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.
Beilstein J. Org. Chem. 2013, 9, 1448–1454, doi:10.3762/bjoc.9.164
Graphical Abstract
Figure 1: Time-resolved CIDNP measurements on a sample of 5 × 10−3 M DES in acetonitrile-d3 sensitized by 2 ×...
Figure 2: Eyring plots of the self-exchange rate constants kex for DES (open circles and broken line; linear ...
Beilstein J. Org. Chem. 2013, 9, 800–808, doi:10.3762/bjoc.9.91
Graphical Abstract
Scheme 1: Photoinduced electron transfer as an access to radical chemistry.
Figure 1: Reduction potential (versus SCE) of the ground and excited state of acceptors and oxidation potenti...
Figure 2: UV-monitoring of: (a) a 2 × 10−4 M solution of TCB in the presence of Bu4Sn (10−2 M) and (b) a 1.5 ...
Figure 3: Absorption spectra of a freeze–pump–thaw deoxygenated MeCN solution irradiated at 313 nm of (a) 1,2...
Scheme 2: Mechanistic scheme.
Figure 4: Thermodynamics of the redox processes discussed (solid arrows represent exergonic electron donation...
Beilstein J. Org. Chem. 2013, 9, 437–446, doi:10.3762/bjoc.9.46
Graphical Abstract
Scheme 1: Mechanism explaining the CIDNP effects in sensitized hydrogen abstractions from tertiary aliphatic ...
Figure 1: Time-resolved CIDNP in sensitized (sensitizers xanthone (XA), benzophenone (BP), or anthraquinone (...
Figure 2: Influence of the laser intensity E on the observed exchange-rate constant kex (DABCO) (main plot) a...
Scheme 2: Pathways from the free radicals to the product.
Figure 3: Time-resolved CIDNP signals of the 18 equivalent β protons (d, 0.98 ppm) of triisopropylamine (TIPA...
Figure 4: Eyring plots for the self-exchange rate constants kex (TIPA) of triisopropylamine (TIPA) sensitized...
Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225
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.
Beilstein J. Org. Chem. 2012, 8, 1305–1311, doi:10.3762/bjoc.8.149
Graphical Abstract
Scheme 1: Enantiodifferentiating photoisomerizations of 1Z and 2ZZ sensitized by β- and γ-cyclodextrin nanosp...
Scheme 2: Representative enantiodifferentiating photosensitization of 1Z and 2ZZ with conventional and supram...
Figure 1: (a) Circular dichroism spectra of 3 (67 μg/mL) (black), 4 (67 μg/mL) (red) and 5 (50 μg/mL) (blue) ...
Figure 2: Circular dichroism spectra of 3 (67 μg/mL) (a) in water at pH 1.9 (black), 4.0 (red), 7.5 (green) a...
Beilstein J. Org. Chem. 2011, 7, 1158–1163, doi:10.3762/bjoc.7.134
Graphical Abstract
Figure 1: Schematic the for contacting modes of biphasic gas–liquid in (a) batch reactor, (b) dual-channel, a...
Figure 2: Optical image of the triple-channel microreactor (for demonstration purposes, the inner channel for...
Figure 3: Photosensitized oxygenation in the triple-channel microreactor.
Scheme 1: Photosensitized oxygenation of citronellol (a key step in the synthesis of rose oxide).
Beilstein J. Org. Chem. 2011, 7, 278–289, doi:10.3762/bjoc.7.37
Graphical Abstract
Scheme 1: Photorearrangements of dibenzobarrelenes 1a and 1b.
Scheme 2: Stereoselective DPM rearrangement of chiral salts in the solid-state.
Scheme 3: Synthesis of ureido- and thioureido-substituted dibenzobarrelene derivatives 1e–i.
Scheme 4: Di-π-methane rearrangements of ureido- and thioureido-substituted dibenzobarrelene derivatives 1h a...
Figure 1: Photometric titration of A) tetrabutylammonium chloride (TBAC) to 1h (c1h = 50 µM) and of B) tetrab...
Figure 2: Structures of chiral additives employed in DPM rearrangements.
Figure 3: Structure of anthracene–thiourea conjugate 4.
Figure 4: Proposed structure of the complex between 1h and mandelate SMD.
Beilstein J. Org. Chem. 2011, 7, 270–277, doi:10.3762/bjoc.7.36
Graphical Abstract
Scheme 1: Photoinduced domino reaction of adamantylphthalimide.
Scheme 2: Synthesis of homoadamantylphthalimide 5.
Figure 1: Molecular structure of 5, the geometry optimization was performed by use of DFT B3LYP/6-31G.
Scheme 3: Products after irradiation of 5.
Scheme 4: Proposed mechanism for the photochemical transformation of 5.
Beilstein J. Org. Chem. 2011, 7, 119–126, doi:10.3762/bjoc.7.17
Graphical Abstract
Scheme 1: Photorearrangements of dibenzobarrelene (DBB).
Figure 1: General structure of pyrrolidinium-annelated dibenzosemibullvalenes (pyDBS).
Scheme 2: Synthesis of dibenzobarrelene derivatives 2a–g.
Scheme 3: Di-π-methane rearrangements of dibenzobarrelene derivatives 2a–f (counter ions omitted for clarity)....
Scheme 4: Di-π-methane rearrangement of dibenzobarrelene derivative 2g.
Scheme 5: Synthesis and solid-state photoreactivity of the sulfonate salt 2b-4.
Scheme 6: Phase-transfer catalyzed alkylation reactions (see Table 1 for details).