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Search for "1,2,4,5-tetraoxanes" in Full Text gives 3 result(s) in Beilstein Journal of Organic Chemistry.
Syntheses and medicinal chemistry of spiro heterocyclic steroids
- Laura L. Romero-Hernández,
- Ana Isabel Ahuja-Casarín,
- Penélope Merino-Montiel,
- Sara Montiel-Smith,
- José Luis Vega-Báez and
- Jesús Sandoval-Ramírez
Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152
- peroxide–hydrochloric acid. A subsequent reaction of the resulting compound with simple ketones in the presence of sulfuric acid produced steroidal 1,2,4,5-tetraoxanes 170 possessing an ester functionality. The unsubstituted ketones gave a single product as expected, while those with substituted precursors
Graphical Abstract
Figure 1: Steroidal spiro heterocycles with remarkable pharmacological activity.
Scheme 1: Synthesis of the spirooxetanone 2. a) t-BuOK, THF, rt, 16%.
Scheme 2: Synthesis of the 17-spirooxetane derivative 7. a) HC≡C(CH2)2CH2OTBDPS, n-BuLi, THF, BF3·Et2O, −78 °...
Scheme 3: Pd-catalyzed carbonylation of steroidal alkynols to produce α-methylene-β-lactones at C-3 and C-17 ...
Scheme 4: Catalyst-free protocol to obtain functionalized spiro-lactones by an intramolecular C–H insertion. ...
Scheme 5: One-pot procedure from dienamides to spiro-β-lactams. a) 1. Ac2O, DMAP, Et3N, CH2Cl2, 2. malononitr...
Scheme 6: Spiro-γ-lactone 20 afforded from 7α-alkanamidoestrone derivative 17. a) HC≡CCH2OTHP, n-BuLi, THF, –...
Scheme 7: Synthesis of the 17-spiro-γ-lactone 23, a key intermediate to obtain spironolactone. a) Ethyl propi...
Scheme 8: Synthetic pathway to obtain 17-spirodihydrofuran-3(2H)-ones from 17-oxosteroids. a) 1-Methoxypropa-...
Scheme 9: One-pot procedure to obtain 17-spiro-2H-furan-3-one compounds. a) NaH, diethyl oxalate, benzene, rt...
Scheme 10: Synthesis of 17-spiro-2H-furan-3-one derivatives. a) RCH=NOH, N-chlorosuccinimide/CHCl3, 99%; b) H2...
Scheme 11: Intramolecular condensation of a γ-acetoxy-β-ketoester to synthesize spirofuranone 37. a) (CH3CN)2P...
Scheme 12: Synthesis of spiro 2,5-dihydrofuran derivatives. a) Allyl bromide, DMF, NaH, 0 °C to rt, 93%; b) G-...
Scheme 13: First reported synthesis of C-16 dispiropyrrolidine derivatives. a) Sarcosine, isatin, MeOH, reflux...
Scheme 14: Cycloadducts 47 with antiproliferative activity against human cancer cell lines. a) 1,4-Dioxane–MeO...
Scheme 15: Spiropyrrolidine compounds generated from (E)-16-arylidene steroids and different ylides. a) Acenap...
Scheme 16: 3-Spiropyrrolidines 52a–c obtained from ketones 50a–c. a) p-Toluenesulfonyl hydrazide, MeOH, rt; b)...
Scheme 17: 16-Spiropyrazolines from 16-methylene-13α-estrone derivatives. a) AgOAc, toluene, rt, 78–81%.
Scheme 18: 6-Spiroimidazolines 57 synthesized by a one-pot multicomponent reaction. a) R3-NC, T3P®, DMSO, 70 °...
Scheme 19: Synthesis of spiro-1,3-oxazolines 60, tested as progesterone receptor antagonist agents. a) CF3COCF3...
Scheme 20: Synthesis of spiro-1,3-oxazolidin-2-ones 63 and 66a,b. a) RNH2, EtOH, 70 °C, 70–90%; b) (CCl3O)2CO,...
Scheme 21: Formation of spiro 1,3-oxazolidin-2-one and spiro 2-substituted amino-4,5-dihydro-1,3-oxazoles from ...
Scheme 22: Synthesis of diastereomeric spiroisoxazolines 74 and 75. a) Ar-C(Cl)=N-OH, DIPEA, toluene, rt, 74 (...
Scheme 23: Spiro 1,3-thiazolidine derivatives 77–79 obtained from 2α-bromo-5α-cholestan-3-one 76. a) 2-aminoet...
Scheme 24: Method for the preparation of derivative 83. a) Benzaldehyde, MeOH, reflux, 77%; b) thioglycolic ac...
Scheme 25: Synthesis of spiro 1,3-thiazolidin-4-one derivatives from steroidal ketones. a) Aniline, EtOH, refl...
Scheme 26: Synthesis of spiro N-aryl-1,3-thiazolidin-4-one derivatives 91 and 92. a) Sulfanilamide, DMF, reflu...
Scheme 27: 1,2,4-Trithiolane dimers 94a–e selectively obtained from carbonyl derivatives. a) LR, CH2Cl2, reflu...
Scheme 28: Spiro 1,2,4-triazolidin-3-ones synthesized from semicarbazones. a) H2O2, CHCl3, 0 °C, 82–85%.
Scheme 29: Steroidal spiro-1,3,4-oxadiazoline 99 obtained in two steps from cholest-5-en-3-one (97). a) NH2NHC...
Scheme 30: Synthesis of spiro-1,3,4-thiadiazoline 101 by cyclization and diacetylation of thiosemicarbazone 100...
Scheme 31: Mono- and bis(1,3,4-thiadiazolines) obtained from estrane and androstane derivatives. a) H2NCSNHNH2...
Scheme 32: Different reaction conditions to synthesize spiro-1,3,2-oxathiaphospholanes 108 and 109.
Scheme 33: Spiro-δ-lactones derived from ADT and epi-ADT as inhibitors of 17β-HSDs. a) CH≡C(CH2)2OTHP, n-BuLi,...
Scheme 34: Spiro-δ-lactams 123a,b obtained in a five-step reaction sequence. a) (R)-(+)-tert-butylsulfinamide,...
Scheme 35: Steroid-coumarin conjugates as fluorescent DHT analogues to study 17-oxidoreductases for androgen m...
Scheme 36: 17-Spiro estradiolmorpholinones 130 bearing two types of molecular diversity. a) ʟ- or ᴅ-amino acid...
Scheme 37: Steroidal spiromorpholinones as inhibitors of enzyme 17β-HSD3. a) Methyl ester of ʟ- or ᴅ-leucine, ...
Scheme 38: Steroidal spiro-morpholin-3-ones achieved by N-alkylation or N-acylation of amino diols 141, follow...
Scheme 39: Straightforward method to synthesize a spiromorpholinone derivative from estrone. a) BnBr, K2CO3, CH...
Scheme 40: Pyrazolo[4,3-e][1,2,4]-triazine derivatives 152–154. a) 4-Aminoantipyrine, EtOH/DMF, reflux, 82%; b...
Scheme 41: One-pot procedure to synthesize spiro-1,3,4-thiadiazine derivatives. a) NH2NHCSCONHR, H2SO4, dioxan...
Scheme 42: 1,2,4-Trioxanes with antimalarial activity. a) 1. O2, methylene blue, CH3CN, 500 W tungsten halogen...
Scheme 43: Tetraoxanes 167 and 168 synthesized from ketones 163, 165 and 166. a) NaOH, iPrOH/H2O, 80 °C, 93%; ...
Scheme 44: 1,2,4,5-Tetraoxanes bearing a steroidal moiety and a cycloalkane. a) 30% H2O2/CH2Cl2/CH3CN, HCl, rt...
Scheme 45: Spiro-1,3,2-dioxaphosphorinanes obtained from estrone derivatives. a) KBH4, MeOH, THF or CH2Cl2; b)...
Scheme 46: Synthesis of steroidal spiro-ε-lactone 183. a) 1. Jones reagent, acetone, 0 °C to rt, 2. ClCOCOCl, ...
Scheme 47: Synthesis of spiro-2,3,4,7-tetrahydrooxepines 185 and 187 derived from mestranol and lynestrenol (38...
Rearrangements of organic peroxides and related processes
- Ivan A. Yaremenko,
- Vera A. Vil’,
- Dmitry V. Demchuk and
- Alexander O. Terent’ev
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.
Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products
- Alexander O. Terent'ev,
- Dmitry A. Borisov,
- Vera A. Vil’ and
- Valery M. Dembitsky
Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6
- .10.6 Abstract The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update
- , and antitumor agents. Keywords: cyclic peroxides; 1,2-dioxanes; 1,2-dioxenes; 1,2-dioxolanes; ozonides; 1,2,4,5-tetraoxanes; 1,2,4-trioxanes; 1,2,4-trioxolanes; Introduction Approaches to the synthesis of five and six-membered cyclic peroxides, such as 1,2-dioxolanes I, 1,2,4-trioxolanes (ozonides
- ) II, 1,2-dioxanes III, 1,2-dioxenes IV, 1,2,4-trioxanes V, and 1,2,4,5-tetraoxanes VI, published from 2000 to present are reviewed. These compounds are widely used in synthetic and medicinal chemistry (Figure 1). In the last decade, two reviews on this rapidly progressing field were published by
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).
