Search for "solvent-free conditions" in Full Text gives 143 result(s) in Beilstein Journal of Organic Chemistry.
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, 1269–1301, doi:10.3762/bjoc.12.121
Graphical Abstract
Scheme 1: The Biginelli condensation.
Scheme 2: The Biginelli reaction of β-ketophosphonates catalyzed by ytterbium triflate.
Scheme 3: Trimethylchlorosilane-mediated Biginelli reaction of diethyl (3,3,3-trifluoropropyl-2-oxo)phosphona...
Scheme 4: Biginelli reaction of dialkyl (3,3,3-trifluoropropyl-2-oxo)phosphonate with trialkyl orthoformates ...
Scheme 5: p-Toluenesulfonic acid-promoted Biginelli reaction of β-ketophosphonates, aryl aldehydes and urea.
Scheme 6: General Kabachnik–Fields reaction for the synthesis of α-aminophosphonates.
Scheme 7: Phthalocyanine–AlCl catalyzed Kabachnik–Fields reaction of N-Boc-piperidin-4-one with diethyl phosp...
Scheme 8: Kabachnik–Fields reaction of isatin with diethyl phosphite and benzylamine.
Scheme 9: Magnetic Fe3O4 nanoparticle-supported phosphotungstic acid-catalyzed Kabachnik–Fields reaction of i...
Scheme 10: The Mg(ClO4)2-catalyzed Kabachnik–Fields reaction of 1-tosylpiperidine-4-one.
Scheme 11: An asymmetric version of the Kabachnik–Fields reaction for the synthesis of α-amino-3-piperidinylph...
Scheme 12: A classical Kabachnik–Fields reaction followed by an intramolecular ring-closing reaction for the s...
Scheme 13: Synthesis of (S)-piperidin-2-phosphonic acid through an asymmetric Kabachnik–Fields reaction.
Scheme 14: A modified diastereoselective Kabachnik–Fields reaction for the synthesis of isoindolin-1-one-3-pho...
Scheme 15: A microwave-assisted Kabachnik–Fields reaction toward isoindolin-1-ones.
Scheme 16: The synthesis of 3-arylmethyleneisoindolin-1-ones through a Horner–Wadsworth–Emmons reaction of Kab...
Scheme 17: An efficient one-pot method for the synthesis of ethyl (2-alkyl- and 2-aryl-3-oxoisoindolin-1-yl)ph...
Scheme 18: FeCl3 and PdCl2 co-catalyzed three-component reaction of 2-alkynylbenzaldehydes, anilines, and diet...
Scheme 19: Three-component reaction of 6-methyl-3-formylchromone (75) with hydrazine derivatives or hydroxylam...
Scheme 20: Three-component reaction of 6-methyl-3-formylchromone (75) with thiourea, guanidinium carbonate or ...
Scheme 21: Three-component reaction of 6-methyl-3-formylchromone (75) with 1,4-bi-nucleophiles in the presence...
Scheme 22: One-pot three-component reaction of 2-alkynylbenzaldehydes, amines, and diethyl phosphonate.
Scheme 23: Lewis acid–surfactant combined catalysts for the one-pot three-component reaction of 2-alkynylbenza...
Scheme 24: Lewis acid catalyzed cyclization of different Kabachnik–Fields adducts.
Scheme 25: Three-component synthesis of N-arylisoquinolone-1-phosphonates 119.
Scheme 26: CuI-catalyzed three-component tandem reaction of 2-(2-formylphenyl)ethanones with aromatic amines a...
Scheme 27: Synthesis of 1,5-benzodiazepin-2-ylphosphonates via ytterbium chloride-catalyzed three-component re...
Scheme 28: FeCl3-catalyzed four-component reaction for the synthesis of 1,5-benzodiazepin-2-ylphosphonates.
Scheme 29: Synthesis of indole bisphosphonates through a modified Kabachnik–Fields reaction.
Scheme 30: Synthesis of heterocyclic bisphosphonates via Kabachnik–Fields reaction of triethyl orthoformate.
Scheme 31: A domino Knoevenagel/phospha-Michael process for the synthesis of 2-oxoindolin-3-ylphosphonates.
Scheme 32: Intramolecular cyclization of phospha-Michael adducts to give dihydropyridinylphosphonates.
Scheme 33: Synthesis of fused phosphonylpyrans via intramolecular cyclization of phospha-Michael adducts.
Scheme 34: InCl3-catalyzed three-component synthesis of (2-amino-3-cyano-4H-chromen-4-yl)phosphonates.
Scheme 35: Synthesis of phosphonodihydropyrans via a domino Knoevenagel/hetero-Diels–Alder process.
Scheme 36: Multicomponent synthesis of phosphonodihydrothiopyrans via a domino Knoevenagel/hetero-Diels–Alder ...
Scheme 37: One-pot four-component synthesis of 1,2-dihydroisoquinolin-1-ylphosphonates under multicatalytic co...
Scheme 38: CuI-catalyzed four-component reactions of methyleneaziridines towards alkylphosphonates.
Scheme 39: Ruthenium–porphyrin complex-catalyzed three-component synthesis of aziridinylphosphonates and its p...
Scheme 40: Copper(I)-catalyzed three-component reaction towards 1,2,3-triazolyl-5-phosphonates.
Scheme 41: Three-component reaction of acylphosphonates, isocyanides and dialkyl acetylenedicarboxylate to aff...
Scheme 42: Synthesis of (4-imino-3,4-dihydroquinazolin-2-yl)phosphonates via an isocyanide-based three-compone...
Scheme 43: Silver-catalyzed three-component synthesis of (2-imidazolin-4-yl)phosphonates.
Scheme 44: Three-component synthesis of phosphonylpyrazoles.
Scheme 45: One-pot three-component synthesis of 3-carbo-5-phosphonylpyrazoles.
Scheme 46: A one-pot two-step method for the synthesis of phosphonylpyrazoles.
Scheme 47: A one-pot method for the synthesis of (5-vinylpyrazolyl)phosphonates.
Scheme 48: Synthesis of 1H-pyrrol-2-ylphosphonates via the [3 + 2] cycloaddition of phosphonate azomethine yli...
Scheme 49: Three-component synthesis of 1H-pyrrol-2-ylphosphonates.
Scheme 50: The classical Reissert reaction.
Scheme 51: One-pot three-component synthesis of N-phosphorylated isoquinolines.
Scheme 52: One-pot three-component synthesis of 1-acyl-1,2-dihydroquinoline-2-phosphonates and 2-acyl-1,2-dihy...
Scheme 53: Three-component reaction of pyridine derivatives with ethyl propiolate and dialkyl phosphonates.
Scheme 54: Three-component reactions for the phosphorylation of benzothiazole and isoquinoline.
Scheme 55: Three-component synthesis of diphenyl [2-(aminocarbonyl)- or [2-(aminothioxomethyl)-1,2-dihydroisoq...
Scheme 56: Three-component stereoselective synthesis of 1,2-dihydroquinolin-2-ylphosphonates and 1,2-dihydrois...
Scheme 57: Diphosphorylation of diazaheterocyclic compounds via a tandem 1,4–1,2 addition of dimethyl trimethy...
Scheme 58: Multicomponent reaction of alkanedials, acetamide and acetyl chloride in the presence of PCl3 and a...
Scheme 59: An oxidative domino three-component synthesis of polyfunctionalized pyridines.
Scheme 60: A sequential one-pot three-component synthesis of polysubstituted pyrroles.
Scheme 61: Three-component decarboxylative coupling of proline with aldehydes and dialkyl phosphites for the s...
Scheme 62: Three-component domino aza-Wittig/phospha-Mannich sequence for the phosphorylation of isatin deriva...
Scheme 63: Stereoselective synthesis of phosphorylated trans-1,5-benzodiazepines via a one-pot three-component...
Scheme 64: One-pot three-component synthesis of phosphorylated 2,6-dioxohexahydropyrimidines.
Beilstein J. Org. Chem. 2016, 12, 628–635, doi:10.3762/bjoc.12.61
Graphical Abstract
Figure 1: Parent and supported bifunctional thioureas used in this work.
Scheme 1: Reaction of nitrostyrene with diethyl malonate and 2-ethoxycarbonyl cyclopentanone.
Scheme 2: Reaction of nitrostyrenes with malonates and β-diketones.
Scheme 3: Reaction of nitrostyrenes with β-keto esters and β-dicarbonyl compounds.
Scheme 4: Reaction of nitrostyrenes with α-nitrocyclohexanone and ethyl α-nitropropionate.
Beilstein J. Org. Chem. 2016, 12, 462–495, doi:10.3762/bjoc.12.48
Graphical Abstract
Scheme 1: Activation of carbonyl compounds via enamine and iminium intermediates [2].
Scheme 2: Electronic and steric interactions present in enamine activation mode [2].
Scheme 3: Electrophilic activation of carbonyl compounds by a thiourea moiety.
Scheme 4: Asymmetric synthesis of dihydro-2H-pyran-6-carboxylate 3 using organocatalyst 4 [16].
Scheme 5: Possible hydrogen-bonding for the reaction of (E)-methyl 2-oxo-4-phenylbut-3-enoate [16].
Scheme 6: Asymmetric desymmetrization of 4,4-cyclohexadienones using the Michael addition reaction with malon...
Scheme 7: The enantioselective synthesis of α,α-disubstituted cycloalkanones using catalyst 11 [18].
Scheme 8: The enantioselective synthesis of indolo- and benzoquinolidine compounds through aza-Diels–Alder re...
Scheme 9: Enantioselective [5 + 2] cycloaddition [20].
Scheme 10: Asymmetric synthesis of oxazine derivatives 26 [21].
Scheme 11: Asymmetric synthesis of bicyclo[3.3.1]nonadienone, core 30 present in (−)-huperzine [22].
Scheme 12: Asymmetric inverse electron-demand Diels-Alder reaction catalyzed by amine-thiourea 34 [23].
Scheme 13: Asymmetric entry to morphan skeletons, catalyzed by amine-thiourea 37 [24].
Scheme 14: Asymmetric transformation of (E)-2-nitroallyl acetate [25].
Scheme 15: Proposed way of activation.
Scheme 16: Asymmetric synthesis of nitrobicyclo[3.2.1]octan-2-one derivatives [26].
Scheme 17: Asymmetric tandem Michael–Henry reaction catalyzed by 50 [27].
Scheme 18: Asymmetric Diels–Alder reactions of 3-vinylindoles 51 [29].
Scheme 19: Proposed transition state and activation mode of the asymmetric Diels–Alder reactions of 3-vinylind...
Scheme 20: Desymmetrization of meso-anhydrides by Chin, Song and co-workers [30].
Scheme 21: Desymmetrization of meso-anhydrides by Connon and co-workers [31].
Scheme 22: Asymmetric intramolecular Michael reaction [32].
Scheme 23: Asymmetric addition of malonate to 3-nitro-2H-chromenes 67 [33].
Scheme 24: Intramolecular desymmetrization through an intramolecular aza-Michael reaction [34].
Scheme 25: Enantioselective synthesis of (−)-mesembrine [34].
Scheme 26: A novel asymmetric Michael–Michael reaction [35].
Scheme 27: Asymmetric three-component reaction catalyzed by Takemoto’s catalyst 77 [46].
Scheme 28: Asymmetric domino Michael–Henry reaction [47].
Scheme 29: Asymmetric domino Michael–Henry reaction [48].
Scheme 30: Enantioselective synthesis of derivatives of 3,4-dihydro-2H-pyran 89 [49].
Scheme 31: Asymmetric addition of α,α-dicyano olefins 90 to 3-nitro-2H-chromenes 91 [50].
Scheme 32: Asymmetric three-component reaction producing 2,6-diazabicyclo[2.2.2]octanones 95 [51].
Scheme 33: Asymmetric double Michael reaction producing substituted chromans 99 [52].
Scheme 34: Enantioselective synthesis of multi-functionalized spiro oxindole dienes 106 [53].
Scheme 35: Organocatalyzed Michael aldol cyclization [54].
Scheme 36: Asymmetric synthesis of dihydrocoumarins [55].
Scheme 37: Asymmetric double Michael reaction en route to tetrasubstituted cyclohexenols [56].
Scheme 38: Asymmetric synthesis of α-trifluoromethyl-dihydropyrans 121 [58].
Scheme 39: Tyrosine-derived tertiary amino-thiourea 123 catalyzed Michael hemiaketalization reaction [59].
Scheme 40: Enantioselective entry to bicyclo[3.2.1]octane unit [60].
Scheme 41: Asymmetric synthesis of spiro[4-cyclohexanone-1,3’-oxindoline] 126 [61].
Scheme 42: Kinetic resolution of 3-nitro-2H-chromene 130 [62].
Scheme 43: Asymmetric synthesis of chromanes 136 [63].
Scheme 44: Wang’s utilization of β-unsaturated α-ketoesters 87 [64,65].
Scheme 45: Asymmetric entry to trifluoromethyl-substituted dihydropyrans 144 [66].
Scheme 46: Phenylalanine-derived thiourea-catalyzed domino Michael hemiaketalization reaction [67].
Scheme 47: Asymmetric synthesis of α-trichloromethyldihydropyrans 149 [68].
Scheme 48: Takemoto’s thiourea-catalyzed domino Michael hemiaketalization reaction [69].
Scheme 49: Asymmetric synthesis of densely substituted cyclohexanes [70].
Scheme 50: Enantioselective synthesis of polysubstituted chromeno [4,3-b]pyrrolidine derivatines 157 [71].
Scheme 51: Enantioselective synthesis of spiro-fused cyclohexanone/5-oxazolone scaffolds 162 [72].
Scheme 52: Utilizing 2-mercaptobenzaldehydes 163 in cascade processes [73,74].
Scheme 53: Proposed transition state of the initial sulfa-Michael step [74].
Scheme 54: Asymmetric thiochroman synthesis via dynamic kinetic resolution [75].
Scheme 55: Enantioselective synthesis of thiochromans [76].
Scheme 56: Enantioselective synthesis of chromans and thiochromans synthesis [77].
Scheme 57: Enantioselective sulfa-Michael aldol reaction en route to spiro compounds [78].
Scheme 58: Enantioselective synthesis of 4-aminobenzo(thio)pyrans 179 [79].
Scheme 59: Asymmetric synthesis of tetrahydroquinolines [80].
Scheme 60: Novel asymmetric Mannich–Michael sequence producing tetrahydroquinolines 186 [81].
Scheme 61: Enantioselective synthesis of biologically interesting chromanes 190 and 191 [82].
Scheme 62: Asymmetric tandem Henry–Michael reaction [83].
Scheme 63: An asymmetric synthesis of substituted cyclohexanes via a dynamic kinetic resolution [84].
Scheme 64: Three component-organocascade initiated by Knoevenagel reaction [85].
Scheme 65: Asymmetric Michael reaction catalyzed by catalysts 57 and 211 [86].
Scheme 66: Proposed mechanism for the asymmetric Michael reaction catalyzed by catalysts 57 and 211 [86].
Scheme 67: Asymmetric facile synthesis of hexasubstituted cyclohexanes [87].
Scheme 68: Dual activation catalytic mechanism [87].
Scheme 69: Asymmetric Michael–Michael/aldol reaction catalyzed by catalysts 57, 219 and 214 [88].
Scheme 70: Asymmetric synthesis of substituted cyclohexane derivatives, using catalysts 57 and 223 [89].
Scheme 71: Asymmetric synthesis of substituted piperidine derivatives, using catalysts 223 and 228 [90].
Scheme 72: Asymmetric synthesis of endo-exo spiro-dihydropyran-oxindole derivatives catalyzed by catalyst 232 [91]....
Scheme 73: Asymmetric synthesis of carbazole spiroxindole derivatives, using catalyst 236 [92].
Scheme 74: Enantioselective formal [2 + 2] cycloaddition of enal 209 with nitroalkene 210, using catalysts 23 ...
Scheme 75: Asymmetric synthesis of polycyclized hydroxylactams derivatives, using catalyst 242 [94].
Scheme 76: Asymmetric synthesis of product 243, using catalyst 246 [95].
Scheme 77: Formation of the α-stereoselective acetals 248 from the corresponding enol ether 247, using catalys...
Scheme 78: Selective glycosidation, catalyzed by Shreiner’s catalyst 23 [97].
Beilstein J. Org. Chem. 2015, 11, 2696–2706, doi:10.3762/bjoc.11.290
Graphical Abstract
Figure 1: Chiral ligands utilized in copper-catalyzed alkynylations of cyclic iminium and oxocarbenium ions.
Scheme 1: Li’s alkynylation of acyclic N-arylimines.
Scheme 2: Knochel’s alkynylation of acyclic N-alkylenamines.
Scheme 3: Li’s CDC of tetrahydroisoquinolines and alkynes.
Scheme 4: Li’s alkynylation of N-aryldihydroisoquinolinium ions.
Scheme 5: Schreiber’s alkynylation of N-alkylisoquinolinium ions.
Scheme 6: Ma’s alkynylation of pyridium ions.
Scheme 7: Arndtsen’s alkynylation of cyclic iminium ions.
Scheme 8: Maruoka’s alkynylation of azomethine imines.
Scheme 9: Su’s CDC of tetrahydroisoquinolines and alkynes under ball milling conditions.
Scheme 10: Ma’s A3-coupling.
Scheme 11: Li’s CDC reaction using photoredox catalysis.
Scheme 12: Liu’s CDC reaction of N-carbamoyltetrahydroisoquinolines. T+BF4– = 2,2,6,6-tetramethylpiperidine N-...
Scheme 13: Aponick’s alkynylation of N-carbomoylquinolinium ions using StackPhos as ligand.
Scheme 14: Carreira’s enantioselective, catalytic alkynylation of aldehydes.
Scheme 15: Watson’s alkynylation of isochroman oxocarbenium ions.
Scheme 16: Watson’s alkynylation of chromene oxocarbenium ions.
Scheme 17: Watson’s alkynylation to set diaryl tetrasubstituted stereocenters.
Beilstein J. Org. Chem. 2015, 11, 2318–2325, doi:10.3762/bjoc.11.252
Graphical Abstract
Scheme 1: Various synthetic paths leading to the formation of NHCs.
Scheme 2: Retrosynthetic path for the preparation of symmetrical imidazolium and imidazolinium salts from sim...
Figure 1: Structures of the imidazolium and imidazolinium salts discussed in this study and their acronyms.
Scheme 3: Synthesis of 1,3-dicyclohexylimidazolium tetrafluoroborate (ICy·HBF4).
Scheme 4: Synthesis of 1,3-dibenzylimidazolium tetrafluoroborate (IBn·HBF4).
Scheme 5: Synthesis of 1,3-dimesitylimidazolium salts (IMes·HCl and IMes·HBF4).
Scheme 6: Synthesis of 1,3-dimesitylimidazolinium chloride (SIMes·HCl).
Scheme 7: Synthesis of 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IDip·HCl).
Scheme 8: Synthesis of 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride (SIDip·HCl).
Scheme 9: Synthesis of 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazolium chloride (IDip*·HCl).
Beilstein J. Org. Chem. 2015, 11, 2038–2056, doi:10.3762/bjoc.11.221
Graphical Abstract
Scheme 1: Polymerization of 7-oxanorbornene in water.
Scheme 2: Synthesis of the first well-defined ruthenium carbene.
Scheme 3: Synthesis of Grubbs' 1st generation catalyst.
Figure 1: NHC-Ruthenium complexes and widely used NHC carbenes.
Scheme 4: Access to 21 from the Grubbs’ 1st generation catalyst and its one-pot synthesis.
Scheme 5: Synthesis of supported Hoveyda-type catalyst.
Figure 2: Scope of RCM reactions with supported Hoveyda-type catalyst. Reaction conditions: 24 (5 mol %), non...
Scheme 6: Synthesis of 33 by Hoveyda and Blechert.
Figure 3: Synthesis of chiral Hoveyda–Grubbs type catalyst and its use in RO/CM.
Scheme 7: Synthesis of 41.
Figure 4: RCM reactions in air using 41 as catalyst. Reaction conditions: 41 (5 mol %), MeOH (0.05 M), 22 °C,...
Figure 5: CM-type reactions in air using 41 as catalyst. Reaction conditions: 41 (5 mol %), 22 °C, 12 h, in a...
Figure 6: Grela's complex (54) and reaction scope in air. Reaction conditions: catalyst, substrate (0.25 mmol...
Figure 7: Abell's complex (61) and its RCM reaction scope in air. Reaction condition: 10 mol % of 61, refluxi...
Figure 8: Catalysts used by Meier in air.
Figure 9: Ammonium chloride-tagged complexes.
Figure 10: Scorpio-type complexes.
Scheme 8: Synthesis of Grubbs' 3rd generation catalyst.
Figure 11: Indenylidene complexes.
Figure 12: Commercially available complexes evaluated under air.
Figure 13: Grela's N,N-unsymmetrically substituted complexes.
Scheme 9: Synthesis of phosphite-based catalysts.
Figure 14: Catalysts used by the Cazin group.
Figure 15: RCM scope in air with catalysts 33, 85 and 98a. Reaction conditions: Catalyst, substrate (0.25 mmol...
Figure 16: Synthesis of Schiff base-ruthenium complexes.
Scheme 10: Schiff base–ruthenium complexes synthesized by Verpoort.
Scheme 11: Synthesis of mixed Schiff base–NHC complexes.
Figure 17: Veerport's indenylidene Schiff-base complexes.
Beilstein J. Org. Chem. 2015, 11, 2021–2028, doi:10.3762/bjoc.11.219
Graphical Abstract
Figure 1: Formation of substituted aziridine.
Figure 2: Various strategies for the formation of 2H-azirine.
Scheme 1: Attempted reaction for the synthesis of 3a.
Figure 3: Synthesis of α-amido-1,3-diketone (3a–o). Reaction conditions: α-azidochalcone 1 (1.0 equiv) and ca...
Scheme 2: Plausible mechanism.
Scheme 3: Attempted reaction with acid derivatives.
Scheme 4: Oxazole formation from 3.
Figure 4: Possible isomers for 7.
Scheme 5: Oxazole formation.
Figure 5: Synthesis of highly substituted 2-(trifluoromethyl)oxazoles (8a–e). Reaction conditions: α-azidocha...
Scheme 6: Mechanism for the formation of 8.
Beilstein J. Org. Chem. 2015, 11, 1985–1990, doi:10.3762/bjoc.11.214
Graphical Abstract
Scheme 1: Non-catalyzed addition of P–H species to alkenes.
Figure 1: ORTEP drawing (30% thermal ellipsoid) of phosphine oxide 3d. A CIF file with the crystallographic d...
Scheme 2: Addition of secondary phosphine sulfide to vinyl sulfide under aerobic catalyst-free conditions.
Scheme 3: Putative mechanism.
Beilstein J. Org. Chem. 2015, 11, 1614–1623, doi:10.3762/bjoc.11.176
Graphical Abstract
Scheme 1: Synthesis of cyclic and polycarbonates.
Figure 1: Bifunctional aluminium–salen complexes, including those studied in this work.
Scheme 2: Synthesis of salen ligands 8a and 8b.
Scheme 3: The preparation of aluminum complexes 1, 2 and 10.
Scheme 4: Possible formation of a dinuclear complex from 1 by treatment with H2O and Et3N.
Figure 2: MALDI–TOF spectrum of poly(hexene carbonate) prepared using catalyst 2. The peak at 565 Daltons cor...
Figure 3: GPC trace of poly(cyclohexene carbonate) prepared using catalyst 2. The chromatogram was obtained i...
Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120
Graphical Abstract
Figure 1: Depictions of 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (exTTF) in the (a) neutral for...
Scheme 1: Synthetic route to the target exTTF-based molecular wire 5.
Figure 2: Cyclic voltammograms of compound 5 and pristine exTTF (at concentrations of approximately 0.2 mM) u...
Figure 3: 2D histograms resulting from break junction experiments on an unmodified gold sample (a), OPE3-dith...
Figure 4: 2D histograms corresponding to compound 5 after exposing a gold substrate to the solution of the co...
Figure 5: 2D histograms corresponding to compound 5 after exposing a gold substrate to a solution of the comp...
Figure 6: a) Examples of individual G(z) traces showing clear conductance plateaus. b–e) 2D histograms corres...
Figure 7: Frontier orbitals of compound 5 in the gas phase.
Figure 8: Top a) and hollow b) binding geometries of 5 to a gold cluster in metal–molecule–metal junctions.
Figure 9: Transmission as a function of energy for the top and hollow binding geometries.
Beilstein J. Org. Chem. 2015, 11, 504–513, doi:10.3762/bjoc.11.57
Graphical Abstract
Scheme 1: The key experimental results on the DDC 1 reactions with thioketones 2 [19-21].
Figure 1: Diazo compounds 1 and thioketones 2 used in the study.
Scheme 2: General scheme for reactions of DDC 1 with thiobenzophenone (2a).
Figure 2: Optimized structures of the lowest energy Z,E-conformers of diazo compounds 1a–d.
Scheme 3: Reactions of the intermediate thiocarbonyl ylide 7'd via competative 1,5-EC (a) or 1,3-EC (b) follo...
Beilstein J. Org. Chem. 2014, 10, 2654–2657, doi:10.3762/bjoc.10.278
Graphical Abstract
Figure 1: Targeted modified cyclodextrins.
Scheme 1: Synthesis of bicatenar CDs 4, 5, 6 and 7; a) succinic anhydride, 135 °C, 10 min, 70%; b) phytosphin...
Beilstein J. Org. Chem. 2014, 10, 2513–2520, doi:10.3762/bjoc.10.262
Graphical Abstract
Scheme 1: Preparation of the starting materials.
Figure 1: Amine-based nucleophiles used in the epoxide ring opening reaction.
Scheme 2: Postulated mechanism for the formation of 14a,b.
Beilstein J. Org. Chem. 2014, 10, 1706–1732, doi:10.3762/bjoc.10.179
Graphical Abstract
Figure 1: Selected chemical modifications of natural ribose or 2'-deoxyribose nucleosides leading to the deve...
Scheme 1: (a) Classical Mannich reaction; (b) general structures of selected hydrogen active components and s...
Scheme 2: Reagents and reaction conditions: i. H2O or H2O/EtOH, 60–100 °C, 7 h–10 d; ii. H2, Pd/C or PtO2; ii...
Scheme 3: Reagents and reaction conditions: i. H2O, 90 °C, overnight.
Scheme 4: Reagents and reaction conditions: i. AcOH, H2O, 60 °C, 12 h-5 d; ii. AcOH, H2O, 60 °C, 8 h.
Scheme 5: Reagents and reaction conditions: i. CuBr, THF, reflux, 0.5 h; ii. n-Bu4NF·3H2O, THF, rt, 2 h.
Scheme 6: Reagents and reaction conditions: i. [bmim][PF6], 80 °C, 5–8 h.
Scheme 7: Reagents and reaction conditions: i. EtOH, reflux, 24 h.
Scheme 8: Reagents and reaction conditions: i. NaOAc, H2O, 95 °C, 1–16 h; ii. NaOAc, H2O, 95 °C, 1 h.
Scheme 9: Reagents and reaction conditions: i. a. 37% aq HCl, MeOH; b. NaOAc, 1,4-dioxane, H2O, 100 °C, overn...
Scheme 10: Reagents and reaction conditions: i. DMAP, DCC, MeOH, rt, 1 h.
Scheme 11: The Kabachnik–Fields reaction.
Scheme 12: Reagents and reaction conditions: i. 60 °C, 3 h; ii. 80 °C, 2 h.
Scheme 13: The four-component Ugi reaction.
Scheme 14: Reagents and reaction conditions: i. MeOH, rt, 2–3 d, yields not given.
Scheme 15: Reagents and reaction conditions: i. MeOH/CH2Cl2 (1:1), rt, 24 h, yield not given; ii. 6 N aq HCl, ...
Scheme 16: Reagents and reaction conditions: i. MeOH/H2O, rt, 26 h; ii. aq AcOH, reflux, 50%; iii. reversed ph...
Scheme 17: Reagents and reaction conditions: i. MeOH, rt, 24 h; ii. HCl, MeOH, 0 °C to rt, 6 h, then H2O, rt, ...
Scheme 18: Reagents and reaction conditions: i. DMF/Py/MeOH (1:1:1), rt, 48 h; ii. 10% HCl/MeOH, rt, 30 min.
Scheme 19: Reagents and reaction conditions (R = CH3 or H): i. CH2Cl2/MeOH (2:1), 35–40 °C, 2 d; ii. HF/pyridi...
Scheme 20: Reagents and reaction conditions: i. MeOH, 76%; ii. 80% aq TFA, 100%.
Scheme 21: Reagents and reaction conditions: i. EtOH, rt, 72 h; ii. Zn, aq NaH2PO4, THF, rt, 1 week; then 80% ...
Scheme 22: Reagents and reaction conditions: i. EtOH, rt, 48 h, then silica gel chromatography, 33% for 57 (30...
Scheme 23: Reagents and reaction conditions: i. [bmim]BF4, 80 °C, 4 h; ii. [bmim]BF4, 80 °C, 3 h; iii. [bmim]BF...
Scheme 24: Reagents and reaction conditions: i. [bmim]BF4, 80 °C.
Scheme 25: Reagents and reaction conditions: i. H3PW12O40 (2 mol %), EtOH, 50 °C, 2–15 h; ii. H3PW12O40 (2 mol...
Scheme 26: General scheme of the Biginelli reaction.
Scheme 27: Reagents and reaction conditions: i. EtOH, reflux.
Scheme 28: Reagents and reaction conditions: i. Bu4N+HSO4−, diethylene glycol, 120 °C, 1.5–3 h.
Scheme 29: Reagents and reaction conditions: i. BF3·Et2O, CuCl, AcOH, THF, 65 °C, 24 h; ii. Yb(OTf)3, THF, ref...
Scheme 30: Reagents and reaction conditions: TCT (10 mol %), rt: i. 100 min; ii. 150 min; iii. 140 min.
Scheme 31: Reagents and reaction conditions: i. EtOH, microwave irradiation (300 W), 10 min; ii. EtOH, 75 °C, ...
Scheme 32: The Hantzsch reaction.
Scheme 33: Reagents and reaction conditions: TCT (10 mol %), rt, 80–150 min.
Scheme 34: Reagents and reaction conditions: i. Yb(OTf)3, THF, 90 °C, 12 h; ii. 4 Å molecular sieves, EtOH, 90...
Scheme 35: Reagents and reaction conditions: i. MeOH, 50 °C, 48 h.
Scheme 36: Reagents and reaction conditions: i. MeOH, 25 °C, 5 d.
Scheme 37: Bu4N+HSO4−, diethylene glycol, 80 °C, 1–2 h.
Scheme 38: The three-component carbopalladation of dienes on the example of buta-1,3-diene.
Scheme 39: Reagents and reaction conditions: i. 5 mol % Pd(dba)2, Bu4NCl, ZnCl2, acetonitrile or DMSO, 80 °C o...
Scheme 40: Reagents and reaction conditions: i. 2.5 mol % Pd2(dba)3, tris(2-furyl)phosphine, K2CO3, MeCN or DM...
Scheme 41: Reagents and reaction conditions: i. 2.5 mol % Pd2(dba)3, tris(2-furyl)phosphine, K2CO3, MeCN or DM...
Scheme 42: The three-component Bucherer–Bergs reaction.
Scheme 43: Reagents and reaction conditions: i. MeOH, H2O, 70 °C, 4.5 h; ii. (1) H2, 5% Pd/C, MeOH, 55 °C, 5 h...
Scheme 44: Reagents and reaction conditions: i. pyridine, MgSO4, 100 °C, 28 h, N2; ii. DMF, 70–90 °C, 22–30 h,...
Scheme 45: Reagents and reaction conditions: i. Montmorillonite K-10 clay, microwave irradiation (600 W), 6–10...
Scheme 46: Reagents and reaction conditions: i. Montmorillonite K-10 clay, microwave irradiation (560 W), 6–10...
Scheme 47: Reagents and reaction conditions: i. CeCl3·7H2O (20 mol %), NaI (20 mol %), microwave irradiation (...
Scheme 48: Reagents and reaction conditions: i. PhI(OAc)2 (3 mol %), microwave irradiation (45 °C), 6–9 min.
Scheme 49: Reagents and reaction conditions: i. 117, ethyl pyruvate, TiCl4, dichloromethane, −78 °C, 1 h; then ...
Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106
Graphical Abstract
Scheme 1: Synthesis of P-stereogenic phosphines 5 using menthylphosphinite borane diastereomers 2.
Scheme 2: Enantioselective synthesis of chiral phosphines 10 with ephedrine as a chiral auxiliary.
Scheme 3: Chlorophosphine boranes 11a as P-chirogenic electrophilic building blocks.
Scheme 4: Monoalkylation of phenylphosphine borane 15 with methyl iodide in the presence of Cinchona alkaloid...
Scheme 5: Preparation of tetraphosphine borane 19.
Scheme 6: Using chiral chlorophosphine-boranes 11b as phosphide borane 20 precursors.
Scheme 7: Nickel-catalyzed cross-coupling (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 8: Pd-catalyzed cross-coupling reaction with organophosphorus stannanes 30.
Scheme 9: Copper iodide catalyzed carbon–phosphorus bond formation.
Scheme 10: Thermodynamic kinetic resolution as the origin of enantioselectivity in metal-catalyzed asymmetric ...
Scheme 11: Ru-catalyzed asymmetric phosphination of benzyl and alkyl chlorides 35 with HPPhMe (36a, PHOX = pho...
Scheme 12: Pt-catalyzed asymmetric alkylation of secondary phosphines 36b.
Scheme 13: Different adducts 43 can result from hydrophosphination.
Scheme 14: Pt-catalyzed asymmetric hydrophosphination.
Scheme 15: Intramolecular hydrophosphination of phosphinoalkene 47.
Scheme 16: Organocatalytic asymmetric hydrophosphination of α,β-unsaturated aldehydes 59.
Scheme 17: Preparation of phosphines using zinc organometallics.
Scheme 18: Preparation of alkenylphosphines 71a from alkenylzirconocenes 69 (dtc = N,N-diethyldithiocarbamate,...
Scheme 19: SNAr with P-chiral alkylmethylphosphine boranes 13c.
Scheme 20: Synthesis of QuinoxP 74 (TMEDA = tetramethylethylenediamine).
Scheme 21: Pd-Mediated couplings of a vinyl triflate 76 with diphenylphosphine borane 13e.
Figure 1: Menthone (83) and camphor (84) derived chiral phosphines.
Scheme 22: Palladium-catalyzed cross-coupling reaction of vinyl tosylates 85 and 87 with diphenylphosphine bor...
Scheme 23: Attempt for the enantioselective palladium-catalyzed C–P cross-coupling reaction between an alkenyl...
Scheme 24: Enol phosphates 88 as vinylic coupling partners in the palladium-catalyzed C–P cross-coupling react...
Scheme 25: Nickel-catalyzed cross-coupling in the presence of zinc (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 26: Copper-catalyzed coupling of secondary phosphines with vinyl halide 94.
Scheme 27: Palladium-catalyzed cross-coupling of aryl iodides 97 with organoheteroatom stannanes 30.
Scheme 28: Synthesis of optically active phosphine boranes 100 by cross-coupling with a chiral phosphine boran...
Scheme 29: Palladium-catalyzed P–C cross-coupling reactions between primary or secondary phosphines and functi...
Scheme 30: Enantioselective synthesis of a P-chirogenic phosphine 108.
Scheme 31: Enantioselective arylation of silylphosphine 110 ((R,R)-Et-FerroTANE = 1,1'-bis((2R,4R)-2,4-diethyl...
Scheme 32: Nickel-catalyzed arylation of diphenylphosphine 25d.
Scheme 33: Nickel-catalyzed synthesis of (R)-BINAP 116 (dppe = 1,2-bis(diphenylphosphino)ethane, DABCO = 1,4-d...
Scheme 34: Nickel-catalyzed cross-coupling between aryl bromides 119 and diphenylphosphine (25d) (dppp = 1,3-b...
Scheme 35: Stereocontrolled Pd(0)−Cu(I) cocatalyzed aromatic phosphorylation.
Scheme 36: Preparation of alkenylphosphines by hydrophosphination of alkynes.
Scheme 37: Palladium and nickel-catalyzed addition of P–H to alkynes 125a.
Scheme 38: Palladium-catalyzed asymmetric hydrophosphination of an alkyne 128.
Scheme 39: Ruthenium catalyzed hydrophosphination of propargyl alcohols 132 (cod = 1,5-cyclooctadiene).
Scheme 40: Cobalt-catalyzed hydrophosphination of alkynes 134a (acac = acetylacetone).
Scheme 41: Tandem phosphorus–carbon bond formation–oxyfunctionalization of substituted phenylacetylenes 125c (...
Scheme 42: Organolanthanide-catalyzed intramolecular hydrophosphination/cyclization of phosphinoalkynes 143.
Scheme 43: Hydrophosphination of alkynes 134c catalyzed by ytterbium-imine complexes 145 (hmpa = hexamethylpho...
Scheme 44: Calcium-mediated hydrophosphanylation of alkyne 134d.
Scheme 45: Formation and substitution of bromophosphine borane 151.
Scheme 46: General scheme for a nickel or copper catalyzed cross-coupling reaction.
Scheme 47: Copper-catalyzed synthesis of alkynylphosphines 156.
Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46
Graphical Abstract
Scheme 1: General reaction mechanism for Ag(I)-catalyzed A3-coupling reactions.
Scheme 2: A3-coupling reaction catalyzed by polystyrene-supported NHC–silver halides.
Figure 1: Various NHC–Ag(I) complexes used as catalysts for A3-coupling.
Scheme 3: Proposed reaction mechanism for NHC–AgCl catalyzed A3-coupling reactions.
Scheme 4: Liu’s synthesis of pyrrole-2-carboxaldehydes 4.
Scheme 5: Proposed reaction mechanism for Liu’s synthesis of pyrrole-2-carboxaldehydes 4.
Scheme 6: Gold-catalyzed synthesis of propargylamines 1.
Scheme 7: A3-coupling catalyzed by phosphinamidic Au(III) metallacycle 6.
Scheme 8: Gold-catalyzed KA2-coupling.
Scheme 9: A3-coupling applied to aldehyde-containing oligosaccharides 8.
Scheme 10: A3-MCR for the preparation of propargylamine-substituted indoles 9.
Scheme 11: A3-coupling interceded synthesis of furans 12.
Scheme 12: A3/KA2-coupling mediated synthesis of functionalized dihydropyrazoles 13 and polycyclic dihydropyra...
Scheme 13: Au(I)-catalyzed entry to cyclic carbamimidates 17 via an A3-coupling-type approach.
Scheme 14: Proposed reaction mechanism for the Au(I)-catalyzed synthesis of cyclic carbamimidates 17.
Figure 2: Chiral trans-1-diphenylphosphino-2-aminocyclohexane–Au(I) complex 20.
Scheme 15: A3-coupling-type synthesis of oxazoles 21 catalyzed by Au(III)–salen complex.
Scheme 16: Proposed reaction mechanism for the synthesis of oxazoles 21.
Scheme 17: Synthesis of propargyl ethyl ethers 24 by an A3-coupling-type reaction.
Scheme 18: General mechanism of Ag(I)-catalyzed MCRs of 2-alkynylbenzaldehydes, amines and nucleophiles.
Scheme 19: General synthetic pathway to 1,3-disubstituted-1,2-dihydroisoquinolines.
Scheme 20: Synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 29.
Scheme 21: Synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 35 and 36.
Scheme 22: Rh(II)/Ag(I) co-catalyzed synthesis of 1,3-disubstituted-1,2-dihydroisoquinolines 40.
Scheme 23: General synthetic pathway to 2-amino-1,2-dihydroquinolines.
Scheme 24: Synthesis of 2-amino-1,2-dihydroquinolines 47.
Scheme 25: Synthesis of tricyclic H-pyrazolo[5,1-a]isoquinoline 48.
Scheme 26: Synthesis of tricyclic H-pyrazolo[5,1-a]isoquinolines 48.
Scheme 27: Cu(II)/Ag(I) catalyzed synthesis of H-pyrazolo[5,1-a]isoquinolines 48.
Scheme 28: Synthesis of 2-aminopyrazolo[5,1-a]isoquinolines 53.
Scheme 29: Synthesis of 1-(isoquinolin-1-yl)guanidines 55.
Scheme 30: Ag(I)/Cu(I) catalyzed synthesis of 2-amino-H-pyrazolo[5,1-a]isoquinolines 58.
Scheme 31: Ag(I)/Ni(II) co-catalyzed synthesis of 3,4-dihydro-1H-pyridazino[6,1-a]isoquinoline-1,1-dicarboxyla...
Scheme 32: Ag(I) promoted activation of the α-carbon atom of the isocyanide group.
Scheme 33: Synthesis of dihydroimidazoles 65.
Scheme 34: Synthesis of oxazoles 68.
Scheme 35: Stereoselective synthesis of chiral butenolides 71.
Scheme 36: Proposed reaction mechanism for the synthesis of butenolides 71.
Scheme 37: Stereoselective three-component approach to pirrolidines 77 by means of a chiral auxiliary.
Scheme 38: Stereoselective three-component approach to pyrrolidines 81 and 82 by means of a chiral catalyst.
Scheme 39: Synthesis of substituted five-membered carbocyles 86.
Scheme 40: Synthesis of regioisomeric arylnaphthalene lactones.
Scheme 41: Enantioselective synthesis of spiroacetals 96 by Fañanás and Rodríguez [105].
Scheme 42: Enantioselective synthesis of spiroacetals 101 by Gong [106].
Scheme 43: Synthesis of polyfunctionalized fused bicyclic ketals 103 and bridged tricyclic ketals 104.
Scheme 44: Proposed reaction mechanism for the synthesis of ketals 103 and 104.
Scheme 45: Synthesis of β-alkoxyketones 108.
Scheme 46: Synthesis of N-methyl-1,4-dihydropyridines 112.
Scheme 47: Synthesis of tetrahydrocarbazoles 115–117.
Scheme 48: Plausible reaction mechanism for the synthesis of tetrahydrocarbazoles 115–117.
Scheme 49: Carboamination, carboalkoxylation and carbolactonization of terminal alkenes.
Scheme 50: Oxyarylation of alkenes with arylboronic acids and Selectfluor as reoxidant.
Scheme 51: Proposed reaction mechanism for oxyarylation of alkenes.
Scheme 52: Oxyarylation of alkenes with arylsilanes and Selectfluor as reoxidant.
Scheme 53: Oxyarylation of alkenes with arylsilanes and IBA as reoxidant.
Beilstein J. Org. Chem. 2014, 10, 466–470, doi:10.3762/bjoc.10.44
Graphical Abstract
Scheme 1: Synthesis and conversion of 3,4-dihydro-2H-pyrrole-2-carbonitriles 6.
Beilstein J. Org. Chem. 2014, 10, 384–393, doi:10.3762/bjoc.10.36
Graphical Abstract
Scheme 1: Conventional (from the left) and decarboxylative (from the right) Pd-catalyzed Sonogashira coupling...
Scheme 2: Protection of propiolic acid with acetone.
Beilstein J. Org. Chem. 2013, 9, 2751–2761, doi:10.3762/bjoc.9.309
Graphical Abstract
Figure 1: Thioketones 1 and diazodicarbonyl compounds 2.
Figure 2: ORTEP plot [17] of the molecular structure of the 1,3-oxathiole 3a (50% probability ellipsoids; arbitra...
Scheme 1: Reaction of diazocarbonyl compounds 2a,c,e with adamantane-2-thione (1b).
Scheme 2: Three possible pathways A, B and C for the formation of 1,3-oxathioles 3,7 and thiiranes 5 and 8 fr...
Scheme 3: Two competitive transformations of dibenzoyldiazomethane (2b) at 80 °С leading to 3b and 4b.
Scheme 4: Interconversion of 1,3-oxathiole 3e and C=S ylide 6e’ accompanied by 1,3-electrocyclization and des...
Figure 3: Energy profile for the transformation of 1,3-oxathiole 3e to alkene 5e. Relative free energies (kca...
Beilstein J. Org. Chem. 2013, 9, 2451–2456, doi:10.3762/bjoc.9.283
Graphical Abstract
Figure 1: SN2 reaction of activated alkyl fluorides and calculated transition state for the reaction of morph...
Figure 2: Proposed activation of C–F bonds mediated by a triol.
Beilstein J. Org. Chem. 2013, 9, 2344–2353, doi:10.3762/bjoc.9.269
Graphical Abstract
Scheme 1: Synthesis of pyrrole-fused isocoumarins.
Scheme 2: Reaction scheme for the synthesis of pyrrole-fused isocoumarins.
Figure 1: ORTEP diagram of 8c with atom numbering scheme. Thermal ellipsoids are shown at 50% probability wit...
Scheme 3: Mechanism of formation of isocoumarins 5 or 8 on the surface of SSA.
Figure 2: Reusability of SSA for the synthesis of pyrrole-fused isocoumarins.
Beilstein J. Org. Chem. 2013, 9, 2002–2008, doi:10.3762/bjoc.9.235
Graphical Abstract
Scheme 1: Microwave assisted synthesis of arylgold compounds.
Figure 1: Synthesis of arylgold compoundsa,b. aChlorogold precursor (0.32–0.37 mmol), 2 equiv arylboronic aci...
Figure 2: Hydrophenoxylation of alkynesa,b. aAlkyne (0.28 mmol), phenol (0.56 mmol), 130 °C, 20 min, no solve...
Scheme 2: Regioselectivity of the addition reaction using arylgold precatalysts. Alkyne (0.28 mmol), phenol (...
Beilstein J. Org. Chem. 2013, 9, 1388–1396, doi:10.3762/bjoc.9.155
Graphical Abstract
Scheme 1: Sketch illustrating preparation of the Au@HS-CNC catalyst.
Figure 1: Au4f and S2p XPS spectra of the Au@HS-CNC (4.4 mol %) catalyst.
Figure 2: TEM pictures of the HS-NCC and Au@HS-CNC (4.4 mol %) catalyst (scale bar: 5 nm).
Figure 3: Thermogravimetric behavior of the Au@HS-CNC (4.4 mol %) catalyst (A) and CNC (B).
Figure 4: FT-IR spectra of CNC, HS-CNC, and Au@HS-CNC (4.4 mol %) catalyst.
Figure 5: Solid-state 13C NMR spectra of the CNC and Au@HS-CNC (4.4 mol %) catalyst.
Figure 6: Recycling test of Au@HS-CNC (4.4 mol %) catalyst for the three-component coupling of formaldehyde, ...
Beilstein J. Org. Chem. 2013, 9, 786–790, doi:10.3762/bjoc.9.89
Graphical Abstract
Scheme 1: Literature preparations of symmetric, meso-substituted BODIPY dyes.
Scheme 2: Expeditious synthesis of dye 1.
Scheme 3: 5-minute synthesis of dyes 8 and 9.
Scheme 4: 5-minute synthesis of dye 10.