Search for "diols" in Full Text gives 188 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 526–532, doi:10.3762/bjoc.21.40
Graphical Abstract
Figure 1: A: Structure of cryptophycin-52. B: Cryptophycin-52 derivatives modified with conjugation handles i...
Scheme 1: Synthesis of modified unit B derivatives. a) HNO3, H2SO4, 0 °C, 5 h, 48% (isolated as monohydrate);...
Figure 2: Molecular structure of Boc-ᴅ-Phe(4-NHMe)-OMe 7 as determined by single-crystal X-ray diffraction me...
Scheme 2: Synthesis of cryptophycin diols 24 and 25. a) EDC·HCl, DMAP, NEt3, CH2Cl2, 0 °C to rt, 22 h, 60%; b...
Scheme 3: Three-step diol–epoxide transformation starting from diols 24 and 25. a) (MeO)3CH, pyridinium p-tol...
Beilstein J. Org. Chem. 2025, 21, 340–347, doi:10.3762/bjoc.21.24
Graphical Abstract
Scheme 1: Approaches to the synthesis of naphtho[2,3-b]furan-4,9-diones.
Scheme 2: Approaches to the synthesis of furo[2,3-d]pyrimidin-4(3H)-ones.
Scheme 3: Approaches to the synthesis of furan-containing pyranopyrans and pyranochromenes.
Scheme 4: Reaction of alkyl 3-bromo-3-nitroacrylates 1a,b with 2-hydroxynaphthalene-1,4-dione (2a).
Scheme 5: Reaction of alkyl 3-bromo-3-nitroacrylates 1a,b with 4-hydroxy-7,7-dimethyl-7,8-dihydro-2H-1-benzop...
Scheme 6: Reaction of alkyl 3-bromo-3-nitroacrylates 1a,b with 4-hydroxy-7-methyl-2H,5H-pyrano[4,3-b]pyran-2,...
Scheme 7: Reaction of alkyl 3-bromo-3-nitroacrylates 1a,b with pyrimidine-4,6-diols 2e–g.
Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249
Graphical Abstract
Scheme 1: Organic peroxide initiators in polymer chemistry.
Scheme 2: Synthesis of organic peroxides.
Scheme 3: Richness of radical cascades with species formed from hydroperoxides in redox conditions.
Scheme 4: Co-catalyzed allylic peroxidation of alkenes 1 and 3 by TBHP.
Scheme 5: Allylic peroxidation of alkenes 6 by Pd(II)TBHP.
Scheme 6: Cu(I)-catalyzed allylic peroxidation.
Scheme 7: Enantioselective peroxidation of alkenes 10 with TBHP in the presence of copper(I) compounds.
Scheme 8: Oxidation of α-pinene (12) by the Cu(I)/TBHP system.
Scheme 9: Introduction of the tert-butylperoxy fragment into the α-position of cyclic ketones 15 and 17.
Scheme 10: α-Peroxidation of β-dicarbonyl compounds 19 using the Cu(II)/TBHP system.
Scheme 11: Co-catalyzed peroxidation of cyclic compounds 21 with TBHP.
Scheme 12: Co-, Mn- and Fe-catalyzed peroxidation of 2-oxoindoles 23, barbituric acids 25, and 4-hydroxycoumar...
Scheme 13: Cu-catalyzed and metal-free peroxidation of barbituric acid derivatives 31 and 3,4-dihydro-1,4-benz...
Scheme 14: Electrochemical peroxidation of 1,3-dicarbonyl compounds 35.
Scheme 15: Peroxidation of β-dicarbonyl compounds, cyanoacetic esters and malonic esters 37 by the TBAI/TBHP s...
Scheme 16: Cu-catalyzed peroxidation of malonodinitriles and cyanoacetic esters 39 with TBHP.
Scheme 17: Mn-catalyzed remote peroxidation via trifluromethylation of double bond.
Scheme 18: Cu-catalyzed remote peroxidation via trifluromethylthiolation of double bond.
Scheme 19: Fe-, Mn-, and Ru-catalyzed peroxidation of alkylaromatics 45, 47, 49, and 51 with TBHP.
Scheme 20: Cu-catalyzed peroxidation of diphenylacetonitrile (53) with TBHP.
Scheme 21: Cu-catalyzed peroxidation of benzyl cyanides 60 with TBHP.
Scheme 22: Synthesis of tert-butylperoxy esters 63 from benzyl alcohols 62 using the TBAI/TBHP system.
Scheme 23: Enantioselective peroxidation of 2-phenylbutane (64) with TBHP and chiral Cu(I) complex.
Scheme 24: Photochemical synthesis of peroxides 67 from carboxylic acids 66.
Scheme 25: Photochemical peroxidation of benzylic C(sp3)–H.
Scheme 26: Cu- and Ru-catalyzed peroxidation of alkylamines with TBHP.
Scheme 27: Peroxidation of amides 76 with the TBAI/TBHP system.
Scheme 28: Fe-catalyzed functionalization of ethers 78 with TBHP.
Scheme 29: Synthesis of 4-(tert-butylperoxy)-5-phenyloxazol-2(3H)-ones 82 from benzyl alcohols 80 and isocyana...
Scheme 30: Fe- and Co-catalyzed peroxidation of alkanes with TBHP.
Scheme 31: Rh-catalyzed tert-butylperoxy dienone synthesis with TBHP.
Scheme 32: Rh- and Cu-catalyzed phenolic oxidation with TBHP.
Scheme 33: Metal-free peroxidation of phenols 94.
Scheme 34: Cu-catalyzed alkylation–peroxidation of acrylonitrile.
Scheme 35: Cu-catalyzed cycloalkylation–peroxidation of coumarins 99.
Scheme 36: Metal-free cycloalkylation–peroxidation of coumarins 102.
Scheme 37: Difunctionalization of indene 104 with tert-butylperoxy and alkyl groups.
Scheme 38: Acid-catalyzed radical addition of ketones (108, 111) and TBHP to alkenes 107 and acrylates 110.
Scheme 39: Cu-catalyzed alkylation–peroxidation of alkenes 113 with TBHP and diazo compounds 114.
Scheme 40: Cobalt(II)-catalyzed addition of TBHP and 1,3-dicarbonyl compound 116 to alkenes 117.
Scheme 41: Cu(0)- or Co(II)-catalyzed addition of TBHP and alcohols 120 to alkenes 119.
Scheme 42: Fe-catalyzed functionalization of allenes 122 with TBHP.
Scheme 43: Fe-catalyzed alkylation–peroxidation of alkenes 125 and 127.
Scheme 44: Fe- and Co-catalyzed alkylation–peroxidation of alkenes 130, 133 and 134 with TBHP and aldehydes as...
Scheme 45: Carbonylation–peroxidation of alkenes 137, 140, 143 with hydroperoxides and aldehydes.
Scheme 46: Carbamoylation–peroxidation of alkenes 146 with formamides and TBHP.
Scheme 47: TBAB-catalyzed carbonylation–peroxidation of alkenes.
Scheme 48: VOCl2-catalyzed carbonylation–peroxidation of alkenes 152.
Scheme 49: Acylation–peroxidation of alkenes 155 with aldehydes 156 and TBHP using photocatalysis.
Scheme 50: Cu-catalyzed peroxidation of styrenes 158.
Scheme 51: Fe-catalyzed acylation-peroxidation of alkenes 161 with carbazates 160 and TBHP.
Scheme 52: Difunctionalization of alkenes 163, 166 with TBHP and (per)fluoroalkyl halides.
Scheme 53: Difunctionalization of alkenes 169 and 172 with hydroperoxides and sodium (per)fluoromethyl sulfina...
Scheme 54: Trifluoromethylation–peroxidation of styrenes 175 using MOF Cu3(BTC)2 as a catalyst.
Scheme 55: Difunctionalization of alkenes 178 with tert-butylperoxy and dihalomethyl fragments.
Scheme 56: Difunctionalization of alkenes 180 with the tert-butylperoxy and dihalomethyl moieties.
Scheme 57: The nitration–peroxidation of alkenes 182 with t-BuONO and TBHP.
Scheme 58: Azidation–peroxidation of alkenes 184 with TMSN3 and TBHP.
Scheme 59: Co-catalyzed bisperoxidation of butadiene 186.
Scheme 60: Bisperoxidation of styrene (189) and acrylonitrile (192) with TBHP by Minisci.
Scheme 61: Mn-catalyzed synthesis of bis(tert-butyl)peroxides 195 from styrenes 194.
Scheme 62: Bisperoxidation of arylidene-9H-fluorenes 196 and 3-arylidene-2-oxoindoles 198 with TBHP under Mn-c...
Scheme 63: Synthesis of bisperoxides from styrenes 200 and 203 using the Ru and Rh catalysis.
Scheme 64: Iodine-catalyzed bisperoxidation of styrenes 206.
Scheme 65: Synthesis of di-tert-butylperoxyoxoindoles 210 from acrylic acid anilides 209 using a Pd(II)/TBHP o...
Scheme 66: Pinolation/peroxidation of styrenes 211 catalyzed by Cu(I).
Scheme 67: TBAI-catalyzed acyloxylation–peroxidation of alkenes 214 with carboxylic acids and TBHP.
Scheme 68: Difunctionalization of alkenes 217 with TBHP and water or alcohols.
Scheme 69: TBAI-catalyzed hydroxyperoxidation of 1,3-dienes 220.
Scheme 70: Hydroxyperoxidation of 1,3-dienes 220.
Scheme 71: Iodination/peroxidation of alkenes 223 with I2 and hydroperoxides.
Scheme 72: The reactions of cyclic enol ethers 226 and 228 with I2/ROOH system.
Scheme 73: Synthesis of 1-(tert-butylperoxy)-2-iodoethanes 231.
Scheme 74: Synthesis of 1-iodo-2-(tert-butylperoxy)ethanes 233.
Scheme 75: Cu-catalyzed phosphorylation–peroxidation of alkenes 234.
Scheme 76: Co-catalyzed phosphorylation–peroxidation of alkenes 237.
Scheme 77: Ag-catalyzed sulfonylation–peroxidation of alkenes 241.
Scheme 78: Co-catalyzed sulfonylation–peroxidation of alkenes 244.
Scheme 79: Synthesis of α/β-peroxysulfides 248 and 249 from styrenes 247.
Scheme 80: Cu-catalyzed trifluoromethylthiolation–peroxidation of alkenes 250 and allenes 252.
Scheme 81: Photocatalytic sulfonyl peroxidation of alkenes 254 via deamination of N-sulfonyl ketimines 255.
Scheme 82: Photoredox-catalyzed 1,4-peroxidation–sulfonylation of enynones 257.
Scheme 83: Cu-catalyzed silylperoxidation of α,β-unsaturated compounds 260 and enynes 261.
Scheme 84: Fe-catalyzed silyl peroxidation of alkenes.
Scheme 85: Cu-catalyzed germyl peroxidation of alkenes 267.
Scheme 86: TBAI-catalyzed intramolecular cyclization of diazo compounds 269 with further peroxidation.
Scheme 87: Co-catalyzed three-component coupling of benzamides 271, diazo compounds 272 and TBHP.
Scheme 88: Co-catalyzed esterification-peroxidation of diazo compounds 274 with TBHP and carboxylic acids 275.
Scheme 89: Cu-catalyzed alkylation–peroxidation of α-carbonylimines 277 or ketones 280.
Scheme 90: Mn-catalyzed ring-opening peroxidation of cyclobutanols 282 with TBHP.
Scheme 91: Peroxycyclization of tryptamines 284 with TBHP.
Scheme 92: Radical cyclization–peroxidation of homotryptamines 287.
Scheme 93: Iodine-catalyzed oxidative coupling of indoles 288, cyanoacetic esters and TBHP.
Scheme 94: Summary of metal-catalyzed peroxidation processes.
Beilstein J. Org. Chem. 2024, 20, 2954–2958, doi:10.3762/bjoc.20.248
Graphical Abstract
Scheme 1: Synthesis of the starting materials 16, 17, and 18 for the subsequent Williamson ether synthesis wi...
Scheme 2: Synthesis of perfluoroalkyl ester-functionalized aldehydes 22, 23, and 24. Conditions: a) NIS, TFA,...
Scheme 3: Porphyrin synthesis. a) Rothemund porphyrin synthesis of metal-free porphyrins 26, 27, and 28; b) m...
Beilstein J. Org. Chem. 2024, 20, 2940–2945, doi:10.3762/bjoc.20.246
Graphical Abstract
Figure 1: Selected examples of chiral dopants with high HTPs in their nematic host LC mixture.
Scheme 1: Structure–property relationship of 4,6-diheteroaryl-5,5-difluoro-1,3-dioxanes as potential chiral d...
Scheme 2: The syntheses of chiral 4,6-diphenyl-5,5-difluoro-1,3-dioxanes 3 and 4 as dopants for cholesteric l...
Scheme 3: Synthesis of rac-2 as precursor of rac-3 and rac-4.
Figure 2: Configuration of (R,R)-3 determined by X-ray crystallography.
Figure 3: Configuration of (R,R)-4 determined by X-ray crystallography.
Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233
Graphical Abstract
Figure 1: Various applications of tetrafluoroethylenated molecules.
Scheme 1: Precedent synthetic approaches to optically active compounds possessing a tetrafluoroethylene group...
Scheme 2: Synthetic strategy for preparing fluorine-containing amines via [1,3]-proton shift reactions.
Scheme 3: Preparation of the substrates used in this study.
Scheme 4: Derivatization of (S)-20b to (S)-23b for determining the optical purity of (S)-20b.
Scheme 5: Substrate scope for the present [1,3]-proton shift reaction. aYields are determined by 19F NMR spec...
Scheme 6: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2024, 20, 1880–1893, doi:10.3762/bjoc.20.163
Graphical Abstract
Scheme 1: Description of the 2-heteroarylethylamine scope of the present review featuring appropriate heteroa...
Scheme 2: 2-Aminoethylpyridine derivatives with therapeutic activity.
Scheme 3: 2-Aminoethylfuran derivatives with therapeutic activity.
Scheme 4: 2-Aminoethylthiophene derivatives with therapeutic activity, part 1.
Scheme 5: 2-Aminoethylthiophene derivatives with therapeutic activity, part 2.
Scheme 6: 2-Aminoethylthiophene derivatives with therapeutic activity, part 3.
Scheme 7: 2-Aminoethylpyrrole derivatives with therapeutic activity.
Scheme 8: Histamine metabolic pathway.
Scheme 9: 2-Aminoethylimidazole derivatives with therapeutic activity, part 1. Krel is referred as histamine ...
Scheme 10: Conformationally restricted 2-aminoethylimidazole derivatives with therapeutic activity, part 2.
Scheme 11: 2-Aminoethylimidazole derivatives with therapeutic activity, part 3.
Scheme 12: 2-Aminoethylimidazole derivatives with therapeutic activity, part 4.
Scheme 13: 2-Aminoethylpyrazole derivatives with therapeutic activity.
Scheme 14: 2-Aminoethylisoxazole derivatives with therapeutic activity.
Scheme 15: 2-Aminoethylthiazole derivatives with therapeutic activity.
Scheme 16: 2-Aminoethyloxadiazole derivatives with therapeutic activity.
Scheme 17: 2-Aminoethyltriazole derivatives with therapeutic activity.
Scheme 18: 2-Aminoethyloxadiazole derivatives with therapeutic activity.
Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162
Graphical Abstract
Scheme 1: Mechanism of the GBB reaction.
Scheme 2: Comparison of the performance of Sc(OTf)3 with some RE(OTf)3 in a model GBB reaction. Conditions: a...
Scheme 3: Comparison of the performance of various Brønsted acid catalysts in the synthesis of GBB adduct 6. ...
Scheme 4: Synthesis of Brønsted acidic ionic liquid catalyst 7. Conditions: a) neat, 60 °C, 24 h; b) TfOH, DC...
Scheme 5: Aryliodonium derivatives as organic catalysts in the GBB reaction. In the box the proposed binding ...
Scheme 6: DNA-encoded GBB reaction in micelles made of amphiphilic polymer 13. Conditions: a) 13 (50 equiv), ...
Scheme 7: GBB reaction catalyzed by cyclodextrin derivative 14. Conditions: a) 14 (1 mol %), water, 100 °C, 4...
Scheme 8: Proposed mode of activation of CALB. a) activation of the substrates; b) activation of the imine; c...
Scheme 9: One-pot GBB reaction–Suzuki coupling with a bifunctional hybrid biocatalyst. Conditions: a) Pd(0)-C...
Scheme 10: GBB reaction employing 5-HMF (23) as carbonyl component. Conditions: a) TFA (20 mol %), EtOH, 60 °C...
Scheme 11: GBB reaction with β-C-glucopyranosyl aldehyde 26. Conditions: a) InCl3 (20 mol %), MeOH, 70 °C, 2–3...
Scheme 12: GBB reaction with diacetylated 5-formyldeoxyuridine 29, followed by deacetylation of GBB adduct 30....
Scheme 13: GBB reaction with glycal aldehydes 32. Conditions: a) HFIP, 25 °C, 2–4 h.
Scheme 14: Vilsmeier–Haack formylation of 6-β-acetoxyvouacapane (34) and subsequent GBB reaction. Conditions: ...
Scheme 15: GBB reaction of 4-formlyl-PCP 37. Conditions: a) HOAc or HClO4, MeOH/DCM (2:3), rt, 3 d.
Scheme 16: GBB reaction with HexT-aldehyde 39. Conditions: a) 39 (20 nmol) and amidine (20 μmol), MeOH, rt, 6 ...
Scheme 17: GBB reaction of 2,4-diaminopirimidine 41. Conditions: a) Sc(OTf)3 (20 mol %), MeCN, 120 °C (MW), 1 ...
Scheme 18: Synthesis of N-edited guanine derivatives from 3,6-diamine-1,2,4-triazin-5-one 44. Conditions: a) S...
Scheme 19: Synthesis of 2-aminoimidazoles 49 by a Mannich-3CR followed by a one-pot intramolecular oxidative a...
Scheme 20: On DNA Suzuki–Miyaura reaction followed by GBB reaction. Conditions: a) CsOH, sSPhos-Pd-G2; b) AcOH...
Scheme 21: One-pot cascade synthesis of 5-iminoimidazoles. Conditions: a) Na2SO4, DMF, 220 °C (MW).
Scheme 22: GBB reaction of 5-amino-1H-imidazole-4-carbonile 57. Conditions: a) HClO4 (5 mol %), MeOH, rt, 24 h....
Scheme 23: One-pot cascade synthesis of indole-imidazo[1,2,a]pyridine hybrids. In blue the structural motif in...
Scheme 24: One-pot cascade synthesis of fused polycyclic indoles 67 or 69 from indole-3-carbaldehyde. Conditio...
Scheme 25: One-pot cascade synthesis of linked- and bridged polycyclic indoles from indole-2-carbaldehyde (70)...
Scheme 26: One-pot cascade synthesis of pentacyclic dihydroisoquinolines (X = N or CH). In blue the structural...
Scheme 27: One-pot stepwise synthesis of imidazopyridine-fused benzodiazepines 85. Conditions: a) p-TsOH (20 m...
Scheme 28: One-pot stepwise synthesis of benzoxazepinium-fused imidazothiazoles 89. Conditions: a) Yb(OTf)3 (2...
Scheme 29: One-pot stepwise synthesis of fused imidazo[4,5,b]pyridines 95. Conditions: a) HClO4, MeOH, rt, ove...
Scheme 30: Synthesis of heterocyclic polymers via the GBB reaction. Conditions: a) p-TsOH, EtOH, 70 °C, 24 h.
Scheme 31: One-pot multicomponent reaction towards the synthesis of covalent organic frameworks via the GBB re...
Scheme 32: One-pot multicomponent reaction towards the synthesis of covalent organic frameworks via the GBB re...
Scheme 33: GBB-like multicomponent reaction towards the synthesis of benzothiazolpyrroles (X = S) and benzoxaz...
Scheme 34: GBB-like multicomponent reaction towards the formation of imidazo[1,2,a]pyridines. Conditions: a) I2...
Scheme 35: Post-functionalization of GBB products via Ugi reaction. Conditions a) HClO4, DMF, rt, 24 h; b) MeO...
Scheme 36: Post-functionalization of GBB products via Click reaction. Conditions: a) solvent-free, 150 °C, 24 ...
Scheme 37: Post-functionalization of GBB products via cascade alkyne–allene isomerization–intramolecular nucle...
Scheme 38: Post-functionalization of GBB products via metal-catalyzed intramolecular N-arylation. In red and b...
Scheme 39: Post-functionalization of GBB products via isocyanide insertion (X = N or CH). Conditions: a) HClO4...
Scheme 40: Post-functionalization of GBB products via intramolecular nucleophilic addition to nitriles. Condit...
Scheme 41: Post-functionalization of GBB products via Pictet–Spengler cyclization. Conditions: a) 4 N HCl/diox...
Scheme 42: Post-functionalization of GBB products via O-alkylation. Conditions: a) TFA (20 mol %), EtOH, 120 °...
Scheme 43: Post-functionalization of GBB products via macrocyclization (X = -CH2CH2O-, -CH2-, -(CH2)4-). Condi...
Figure 1: Antibacterial activity of GBB-Ugi adducts 113 on both Gram-negative and Gram-positive strains.
Scheme 44: GBB multicomponent reaction using trimethoprim as the precursor. Conditions: a) Yb(OTf)3 or Y(OTf)3...
Figure 2: Antibacterial activity of GBB adducts 152 against MRSA and VRE; NA = not available.
Figure 3: Antibacterial activity of GBB adduct 153 against Leishmania amazonensis promastigotes and amastigot...
Figure 4: Antiviral and anticancer evaluation of the GBB adducts 154a and 154b. In vitro antiproliferative ac...
Figure 5: Anticancer activity of the GBB-furoxan hybrids 145b, 145c and 145d determined through antiprolifera...
Scheme 45: Synthesis and anticancer activity of the GBB-gossypol conjugates. Conditions: a) Sc(OTf)3 (10 mol %...
Figure 6: Anticancer activity of polyheterocycles 133a and 136a against human neuroblastoma. Clonogenic assay...
Figure 7: Development of GBB-adducts 158a and 158b as PD-L1 antagonists. HTRF assays were carried out against...
Figure 8: Development of imidazo[1,2-a]pyridines and imidazo[1,2-a]pyrazines as TDP1 inhibitors. The SMM meth...
Figure 9: GBB adducts 164a–c as anticancer through in vitro HDACs inhibition assays. Additional cytotoxic ass...
Figure 10: GBB adducts 165, 166a and 166b as anti-inflammatory agents through HDAC6 inhibition; NA = not avail...
Scheme 46: GBB reaction of triphenylamine 167. Conditions: a) NH4Cl (10 mol %), MeOH, 80 °C (MW), 1 h.
Scheme 47: 1) Modified GBB-3CR. Conditions: a) TMSCN (1.0 equiv), Sc(OTf)3 (0.2 equiv), MeOH, 140 °C (MW), 20 ...
Scheme 48: GBB reaction to assemble imidazo-fused heterocycle dimers 172. Conditions: a) Sc(OTf)3 (20 mol %), ...
Figure 11: Model compounds 173 and 174, used to study the acid/base-triggered reversible fluorescence response...
Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152
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...
Beilstein J. Org. Chem. 2024, 20, 1671–1676, doi:10.3762/bjoc.20.148
Graphical Abstract
Scheme 1: Build and release approach for the functionalization of simple precursors. a) General overview. b) ...
Scheme 2: Modularity of the Norrish–Yang cyclization for the synthesis of azetidines.
Scheme 3: Ring-opening reactions using electron-deficient ketones and boronic acids.
Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101
Graphical Abstract
Scheme 1: Biosynthesis of (A) germacrene A and (B) hedycaryol from FPP. Here the abbreviations represent, FPP...
Figure 1: 6-6 and 5-7 bicyclic carbocations formed by protonation and cyclization of germacrene A and hedycar...
Figure 2: Bar plot for the relative free energies of germacrene A and hedycaryol carbocations relative to car...
Figure 3: NCI plot for A (left) and B (right). Blue corresponds to repulsive and yellow represents slightly a...
Figure 4: NCI plots for F and H hedycaryol cations. The C+···OH distances (Å) are shown in black.
Figure 5: Correlation plot relating between the stability of hedycaryols (ΔΔEe) and C+···OH bond distances.
Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98
Graphical Abstract
Scheme 1: General scheme of the borrowing hydrogen (BH) or hydrogen auto-transfer (HA) methodology.
Scheme 2: General scheme for C–N bond formation. A) Traditional cross-couplings with alkyl or aryl halides. B...
Figure 1: Manganese pre-catalysts used for the N-alkylation of amines with alcohols.
Scheme 3: Manganese(I)-pincer complex Mn1 used for the N-alkylation of amines with alcohols and methanol.
Scheme 4: N-Methylation of amines with methanol using Mn2.
Scheme 5: C–N-Bond formation with amines and methanol using PN3P-Mn complex Mn3 reported by Sortais et al. [36]. a...
Scheme 6: Base-assisted synthesis of amines and imines with Mn4. Reaction assisted by A) t-BuOK and B) t-BuON...
Scheme 7: Coupling of alcohols and hydrazine via the HB approach reported by Milstein et al. [38]. aReaction time...
Scheme 8: Proposed mechanism for the coupling of alcohols and hydrazine catalyzed by Mn5.
Scheme 9: Phosphine-free manganese catalyst for N-alkylation of amines with alcohols reported by Balaraman an...
Scheme 10: N-Alkylation of sulfonamides with alcohols.
Scheme 11: Mn–NHC catalyst Mn6 applied for the N-alkylation of amines with alcohols. a3 mol % of Mn6 were used....
Scheme 12: N-Alkylation of amines with primary and secondary alcohols. a80 °C, b100 °C.
Scheme 13: Manganese(III)-porphyrin catalyst for synthesis of tertiary amines.
Scheme 14: Proposed mechanism for the alcohol dehydrogenation with Mn(III)-porphyrin complex Mn7.
Scheme 15: N-Methylation of nitroarenes with methanol using catalyst Mn3.
Scheme 16: Mechanism of manganese-catalyzed methylation of nitroarenes using Mn3 as the catalyst.
Scheme 17: Bidentate manganese complex Mn8 applied for the N-alkylation of primary anilines with alcohols. aOn...
Scheme 18: N-Alkylation of amines with alcohols in the presence of manganese salts and triphenylphosphine as t...
Scheme 19: N-Alkylation of diazo compounds with alcohols using catalyst Mn9.
Scheme 20: Proposed mechanism for the amination of alcohols with diazo compounds catalyzed by catalyst Mn9.
Scheme 21: Mn1 complex-catalyzed synthesis of polyethyleneimine from ethylene glycol and ethylenediamine.
Scheme 22: Bis-triazolylidene-manganese complex Mn10 for the N-alkylation of amines with alcohols.
Figure 2: Manganese complexes applied for C-alkylation reactions of ketones with alcohols.
Scheme 23: General scheme for the C–C bond formation with alcohols and ketones.
Scheme 24: Mn1 complex-catalyzed α-alkylation of ketones with primary alcohols.
Scheme 25: Mechanism for the Mn1-catalyzed alkylation of ketones with alcohols.
Scheme 26: Phosphine-free in situ-generated manganese catalyst for the α-alkylation of ketones with primary al...
Scheme 27: Plausible mechanism for the Mn-catalyzed α-alkylation of ketones with alcohols.
Scheme 28: α-Alkylation of esters, ketones, and amides using alcohols catalyzed by Mn11.
Scheme 29: Mono- and dialkylation of methylene ketones with primary alcohols using the Mn(acac)2/1,10-phenanth...
Scheme 30: Methylation of ketones with methanol and deuterated methanol.
Scheme 31: Methylation of ketones and esters with methanol. a50 mol % of t-BuOK were used, bCD3OD was used ins...
Scheme 32: Alkylation of ketones and secondary alcohols with primary alcohols using Mn4.
Scheme 33: Bidentate manganese-NHC complex Mn6 applied for the synthesis of alkylated ketones using alcohols.
Scheme 34: Mn1-catalyzed synthesis of substituted cycloalkanes by coupling diols and secondary alcohols or ket...
Scheme 35: Proposed mechanism for the synthesis of cycloalkanes via BH method.
Scheme 36: Synthesis of various cycloalkanes from methyl ketones and diols catalyze by Mn13. aReaction time wa...
Scheme 37: N,N-Amine–manganese complex (Mn13)-catalyzed alkylation of ketones with alcohols.
Scheme 38: Naphthyridine‑N‑oxide manganese complex Mn14 applied for the alkylation of ketones with alcohols. a...
Scheme 39: Proposed mechanism of the naphthyridine‑N‑oxide manganese complex (Mn14)-catalyzed alkylation of ke...
Scheme 40: α-Methylation of ketones and indoles with methanol using Mn15.
Scheme 41: α-Alkylation of ketones with primary alcohols using Mn16. aNMR yield.
Figure 3: Manganese complexes used for coupling of secondary and primary alcohols.
Scheme 42: Alkylation of secondary alcohols with primary alcohols catalyzed by phosphine-free catalyst Mn17. a...
Scheme 43: PNN-Manganese complex Mn18 for the alkylation of secondary alcohols with primary alcohols.
Scheme 44: Mechanism for the Mn-pincer catalyzed C-alkylation of secondary alcohols with primary alcohols.
Scheme 45: Upgrading of ethanol with methanol for isobutanol production.
Scheme 46: Mn-Pincer catalyst Mn19 applied for the β-methylation of alcohols with methanol. a2.0 mol % of Mn19...
Scheme 47: Functionalized ketones from primary and secondary alcohols catalyzed by Mn20. aMn20 (5 mol %), NaOH...
Scheme 48: Synthesis of γ-disubstituted alcohols and β-disubstituted ketones through Mn9-catalyzed coupling of...
Scheme 49: Proposed mechanism for the Mn9-catalyzed synthesis of γ-disubstituted alcohols and β-disubstituted ...
Scheme 50: Dehydrogenative coupling of ethylene glycol and primary alcohols catalyzed by Mn4.
Scheme 51: Mn18-cataylzed C-alkylation of unactivated esters and amides with alcohols.
Scheme 52: Alkylation of amides and esters using Mn21.
Scheme 53: α-Alkylation of nitriles with primary alcohols using in situ-generated manganese catalyst.
Scheme 54: Proposed mechanism for the α-alkylation of nitriles with primary alcohols.
Scheme 55: Mn9-catalyzed α-alkylation of nitriles with primary alcohols. a1,4-Dioxane was used as solvent, 24 ...
Figure 4: Manganese complexes used for alkylation of heterocyclic compounds.
Scheme 56: Aminomethylation of aromatic compounds with secondary amines and methanol catalyzed by Mn22.
Scheme 57: Regioselective alkylation of indolines with alcohols catalyzed by Mn9. aMn9 (4 mol %), 48 h.
Scheme 58: Proposed mechanism for the C- and N-alkylation of indolines with alcohols.
Scheme 59: C-Alkylation of methyl N-heteroarenes with primary alcohols catalyzed by Mn1. aTime was 60 h.
Scheme 60: C-Alkylation of oxindoles with secondary alcohols.
Scheme 61: Plausible mechanism for the Mn23-catalyzed C-alkylation of oxindoles with secondary alcohols.
Scheme 62: Synthesis of C-3-alkylated products by coupling alcohols with indoles and aminoalcohols.
Scheme 63: C3-Alkylation of indoles using Mn1.
Scheme 64: C-Methylation of indoles with Mn15 and methanol.
Scheme 65: α-Alkylation of 2-oxindoles with primary and secondary alcohols catalyzed by Mn25. aReaction carrie...
Scheme 66: Dehydrogenative alkylation of indolines with Mn1. aMn1 (5.0 mol %) was used.
Scheme 67: Synthesis of bis(indolyl)methane derivatives from indoles and alcohols catalyzed by Mn26. aMn26 (5....
Scheme 68: One-pot synthesis of pyrimidines via BH.
Scheme 69: Synthesis of pyrroles from alcohols and aminoalcohols using Mn4.
Scheme 70: Synthesis of pyrroles via multicomponent reaction catalyzed by Mn12.
Scheme 71: Friedländer quinoline synthesis using an in situ-generated phosphine-free manganese catalyst.
Scheme 72: Quinoline synthesis using bis-N-heterocyclic carbene-manganese catalyst Mn6.
Scheme 73: Quinoline synthesis using manganese(III)-porphyrin catalyst Mn7.
Scheme 74: Manganese-catalyzed tetrahydroquinoline synthesis via borrowing BH.
Scheme 75: Proposed mechanism for the manganese-catalyzed tetrahydroquinoline synthesis.
Scheme 76: Synthesis of C3-alkylated indoles using Mn24.
Scheme 77: Synthesis of C-3-alkylated indoles using Mn1.
Scheme 78: C–C Bond formation by coupling of alcohols and ylides.
Scheme 79: C-Alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 80: Proposed mechanism for the C-alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 81: α-Alkylation of sulfones using Mn-PNN catalyst Mn28.
Beilstein J. Org. Chem. 2024, 20, 815–822, doi:10.3762/bjoc.20.73
Graphical Abstract
Figure 1: (a) Representative bioactive drimane-type sesquiterpenoids (DMTs). (b) Reported biosynthetic pathwa...
Figure 2: Chemical structures and HPLC analysis. (a) Chemical structures of isolated sesquiterpenes 2–4 from ...
Figure 3: Biosynthesis of drimenol congeners. (a) The cav BGC. (b) Proposed biosynthetic pathway for drimenol...
Figure 4: Substrate scope of CavA. (a) The chemical structures of eight natural products that were used for f...
Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6
Graphical Abstract
Scheme 1: Reaction of 1 with various Michael acceptors (EWG = electron-withdrawing group) forming the zwitter...
Figure 1: 1H NMR spectrum of 2a recorded on a 300 MHz spectrometer in CDCl3 at 23 °C; the inset shows a 3D-mo...
Figure 2: a) Molecular structure of 2a, hydrogen atoms omitted for clarity, thermal ellipsoids drawn at 30% p...
Figure 3: Left: UV–vis spectra of 2a, 2b and 2d in chloroform (straight lines) and in methanol (dotted lines)...
Figure 4: Conversion of 1 (initial c = 0.25 mM) toward 2a, 2b, or 2d in the presence of the respective Michae...
Scheme 2: Proposed mechanism for intramolecular proton transfer in zwitterion formation with Michael acceptor...
Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142
Graphical Abstract
Figure 1: (a, b) Schematics of previous approaches to dehalogenation-based reactions using molecular reductan...
Scheme 1: Selective deiodination of 2-iodobenzyl chloride.
Scheme 2: Reaction mechanisms for the reactions of dimeric reductants (D2) such as (Y-DMBI)2 derivatives with...
Figure 2: (a) A representative temporal evolution of % conversion (blue squares), % toluene yield (red diamon...
Figure 3: Top: UV–vis absorption spectra for the two dimeric reductants in THF emphasizing (a) the different ...
Figure 4: Transient absorption spectra of (a) (N-DMBI)2 in MeCN, (b) (N-DMBI)2 in toluene, and (c) (Cyc-DMBI)2...
Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98
Graphical Abstract
Figure 1: Selected natural products and pharmaceuticals bearing acyloins.
Scheme 1: Strategies for the synthesis of α-trifluoromethyl acyloins.
Scheme 2: Substrate scope. Standard conditions: a solution of alkyl carboxylic acid 1 (0.4 mmol), 2 (0.6 mmol...
Figure 2: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96
Graphical Abstract
Figure 1: Chemical structure of some natural ether lipids (ELs).
Figure 2: Synthesis of lyso-PAF and PAF from 1-O-alkylglycerol [64].
Figure 3: Synthesis of lyso-PAF from 1,3-benzylideneglycerol 3.1 [69].
Figure 4: A) Synthesis of the two enantiomers of octadecylglycerol (4.6 and 4.10) from ᴅ-mannitol (4.1); B) s...
Figure 5: Four-step synthesis of PAF 5.6 from (S)-glycidol [73].
Figure 6: Synthesis of 1-O-alkylglycerol A) from solketal, B) from ᴅ- or ʟ-tartaric acid and the intermediate ...
Figure 7: Synthesis of EL building blocks starting from substituted glycidol 7.1a–c [82].
Figure 8: Synthesis of PAF 8.5 by using phosphoramidite 8.2 [86].
Figure 9: Synthesis of oleyl-PAF 9.7 from ʟ-serine [88].
Figure 10: Synthesis of racemic analogues of lyso-PAF 10.8 and PAF 10.9 featuring a phenyl group between the g...
Figure 11: Synthesis of racemic deoxy-lyso-PAF 11.7 and deoxy-PAF 11.8 [91].
Figure 12: Synthesis of racemic thio-PAF 12.8 [93].
Figure 13: Racemic synthesis of 13.6 to illustrate the modification of the glycerol backbone by adding a methy...
Figure 14: Racemic synthesis of 14.5 as an illustration of the introduction of methyl substituents on the glyc...
Figure 15: Synthesis of functionalized sn-2-acyl chains of PC-EL; A) Steglich esterification or acylation reac...
Figure 16: Synthesis of racemic mc-PAF (16.3), a carbamate analogue of PAF [102].
Figure 17: A) Synthesis of (R)-17.2 and (S)-17.6 starting from (S)-solketal (17.1); B) synthesis of N3-PAF (17...
Figure 18: Modification of the phosphocholine polar head to produce PAF analogues [81].
Figure 19: Racemic PAF analogues 19.3 and 19.5 characterized by the absence of the phosphate group [107].
Figure 20: Synthesis of PIP3-PAF (20.7) [108].
Figure 21: Large-scale synthesis of C18-edelfosine (21.8) [116].
Figure 22: Synthesis of C16-edelfosine (22.10) starting from isopropylidene-ʟ-glyceric acid methyl ester (22.1...
Figure 23: Phosphocholine moiety installation by the use of chlorophosphite 23.2 as key reagent [119].
Figure 24: Synthesis of rac-1-alkyl-2-O-methylglycerol (AMG) [120].
Figure 25: Synthesis of stereocontrolled 1-alkyl-2-O-methyl glycerol 25.9 (AMG) from dimethyl ᴅ-tartrate [81].
Figure 26: A) Racemic synthesis of thioether 26.4 [129,130], B) structure of sulfone analogue 26.5 [129].
Figure 27: Stereocontrolled synthesis of C18-edelfosine thioether analogue 27.8 [118].
Figure 28: Synthesis of thioether 28.4 that include a thiophosphate function [134].
Figure 29: Synthesis of ammonium thioether 29.4 and 29.6 [135].
Figure 30: Synthesis of the N-methylamino analogue of edelfosine 30.6 (BN52211) [138].
Figure 31: Synthesis of 1-desoxy analogues of edelfosine; A) with a saturated alkyl chain; B) synthesis of the...
Figure 32: Stereocontrolled synthesis of edelfosine analogue (S)-32.8 featuring a C18:1 lipid chain [142].
Figure 33: Synthesis of edelfosine analogues with modulation of the lipid chain; A) illustration with the synt...
Figure 34: Synthesis of phospholipid featuring a carbamate function to link the lipid chain to the glycerol un...
Figure 35: Synthesis of sesquiterpene conjugates of phospho glycero ether lipids [148].
Figure 36: Racemic synthesis of methyl-substituted glycerol analogues 36.7 and 36.10: A) synthesis of diether ...
Figure 37: Racemic synthesis of ilmofosine (37.6) [155,156].
Figure 38: A) Stereoselective synthesis of 38.5 via a stereoselective hydroboration reaction; B) synthesis of ...
Figure 39: Racemic synthesis of SRI62-834 (39.6) featuring a spiro-tetrahydrofurane heterocycle in position 2 ...
Figure 40: Racemic synthesis of edelfosine analogue 40.5 featuring an imidazole moiety in sn-2 position [160].
Figure 41: Racemic synthesis of fluorine-functionalized EL: A) Synthesis of 41.6 and B) synthesis of 41.8 [161-163].
Figure 42: A) Synthesis of the β-keto-ester 42.6 that also features a decyl linker between the phosphate and t...
Figure 43: Synthesis of phosphonate-based ether lipids; A) edelfosine phosphonate analogue 43.7 and B) thioeth...
Figure 44: Enantioselective synthesis of phosphonates 44.3 and 44.4 [171].
Figure 45: Racemic synthesis of phosphinate-based ether lipid 45.10 [172].
Figure 46: Racemic synthesis of edelfosine arsonium analogue 46.5 [173].
Figure 47: Synthesis of edelfosine dimethylammonium analogue 47.2 [118].
Figure 48: Synthesis of rac-C18-edelfosine methylammonium analogue 48.4 [176].
Figure 49: A) Synthesis of edelfosine N-methylpyrrolidinium analogue 49.2 or N-methylmorpholinium analogue 49.3...
Figure 50: A) Synthesis of edelfosine’s analogue 50.4 with a PE polar group; B) illustration of a pyridinium d...
Figure 51: A) Synthesis of 51.4 featuring a thiazolium cationic moiety; B) synthesis of thiazolium-based EL 51...
Figure 52: Synthesis of cationic ether lipids 52.3, 52.4 and 52.6 [135,183].
Figure 53: Synthesis of cationic carbamate ether lipid 53.5 [184].
Figure 54: Synthesis of cationic sulfonamide 54.5 [185].
Figure 55: Chemical structure of ONO-6240 (55.1) and SRI-63-119 (55.2).
Figure 56: Synthesis of non-ionic ether lipids 56.2–56.9 [188].
Figure 57: Synthesis of ether lipid conjugated to foscarnet 57.6 [189].
Figure 58: A) Synthesis of ether lipid conjugated to arabinofuranosylcytosine; B) synthesis of AZT conjugated ...
Figure 59: Synthesis of quercetin conjugate to edelfosine [191].
Figure 60: Synthesis of 60.8 (Glc-PAF) [194].
Figure 61: A) Synthesis of amino ether lipid 61.7 functionalized with a rhamnose unit and its amide analogue 6...
Figure 62: A) Synthesis of glucose ether lipid 62.4; B) structure of ether lipid 62.5 possessing a maltose uni...
Figure 63: A) Synthesis of glucuronic methyl ester 63.8; B) structure of cellobiose 63.9 and maltose 63.10 ana...
Figure 64: A) Synthesis of maltosyl glycerolipid 64.7; B) structure of lactose analogue 64.8 prepared followin...
Figure 65: A) Asymmetric synthesis of the aglycone moiety starting from allyl 4-methoxyphenyl ether; B) glycos...
Figure 66: A) Synthesis of ohmline possessing a lactose moiety. B) Structure of other glyco glycero lipids pre...
Figure 67: A) Synthesis of lactose-glycerol ether lipid 67.5; B) analogues possessing a maltose (67.6) or meli...
Figure 68: Synthesis of digalactosyl EL 68.6, A) by using trityl, benzyl and acetyl protecting groups, B) by u...
Figure 69: A) Synthesis of α-ohmline; B) structure of disaccharide ether lipids prepared by using similar meth...
Figure 70: Synthesis of lactose ether lipid 70.3 and its analogue 70.6 featuring a carbamate function as linke...
Figure 71: Synthesis of rhamnopyranoside diether 71.4 [196].
Figure 72: Synthesis of 1-O-hexadecyl-2-O-methyl-3-S-(α-ᴅ-1'-thioglucopyranosyl)-sn-glycerol (72.5) [225].
Figure 73: A) Preparation of lipid intermediate 73.4; B) synthesis of 2-desoxy-C-glycoside 73.10 [226].
Figure 74: Synthesis of galactose-pyridinium salt 74.3 [228].
Figure 75: Synthesis of myo-inositol derivative Ino-C2-PAF (75.10) [230].
Figure 76: A) Synthesis of myo-inositol phosphate building block 76.7; B) synthesis of myo-inositolphosphate d...
Figure 77: A) Synthesis of phosphatidyl-3-desoxy-inositol 77.4; B) synthesis of phosphono-3-desoxyinositol 77.9...
Figure 78: A) Structure of diether phosphatidyl-myo-inositol-3,4-diphosphate 78.1; B) synthesis of phosphatidy...
Figure 79: A) Synthesis of diether-phosphatidyl derivative 79.4 featuring a hydroxymethyl group in place of a ...
Figure 80: Synthesis of Glc-amine-PAF [78].
Figure 81: Synthesis of glucosamine ether lipid 81.4 and its analogues functionalized in position 3 of the ami...
Figure 82: Synthesis of fully deprotected aminoglucoside ether lipid 82.5 [246].
Figure 83: Synthesis of C-aminoglycoside 83.12 using Ramberg–Bäcklund rearrangement as a key step [250].
Figure 84: A) List of the most important glyco lipids and amino glyco lipids included in the study of Arthur a...
Figure 85: Synthesis of mannosamine ether lipid 85.6 [254].
Figure 86: A) Synthesis of glucosamine ether lipids with a non-natural ʟ-glucosamine moiety; B) synthesis of e...
Figure 87: A) Structure of the most efficient anticancer agents 87.1–87.4 featuring a diamino glyco ether lipi...
Figure 88: A) Synthesis of diamino glyco ether lipid 87.4; B) synthesis of bis-glycosylated ether lipid 88.10 [256]....
Figure 89: Synthesis of triamino ether lipid 89.4 [260].
Figure 90: Synthesis of chlorambucil conjugate 90.7 [261].
Figure 91: Three main methods for the preparation of glycerol ether lipid 91.3; A) from solketal and via a tri...
Figure 92: Four different methods for the installation of the phosphocholine polar head group; A) method using...
Figure 93: Illustration of two methods for the installation of saccharides or aminosaccharides; A) O-glycosyla...
Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23
Graphical Abstract
Figure 1: Examples of terpenes containing a bicyclo[3.6.0]undecane motif.
Figure 2: Commercially available first and second generation Grubbs and Hoveyda–Grubbs catalysts.
Figure 3: Examples of strategies to access the fusicoccan and ophiobolin tricyclic core structure by RCM.
Scheme 1: Synthesis of bicyclic core structure 12 of ophiobolin M (13) and cycloaraneosene (14).
Scheme 2: Synthesis of the core structure 21 of ophiobolins and fusicoccanes.
Scheme 3: Ring-closing metathesis attempts starting from thioester 22.
Scheme 4: Total synthesis of ent-fusicoauritone (28).
Figure 4: General structure of ophiobolins and congeners.
Scheme 5: Total synthesis of (+)-ophiobolin A (8).
Scheme 6: Investigation of RCM for the synthesis of ophiobolin A (8). Path A) RCM with TBDPS-protected alcoho...
Scheme 7: Synthesis of the core structure of cotylenin A aglycon, cotylenol (50).
Scheme 8: Synthesis of tricyclic core structure of fusicoccans.
Scheme 9: Total synthesis of (−)-teubrevin G (59).
Scheme 10: Synthesis of the core skeleton 63 of the basmane family.
Scheme 11: Total synthesis of (±)-schindilactone A (68).
Scheme 12: Total synthesis of dactylol (72).
Scheme 13: Ring-closing metathesis for the total synthesis of (±)-asteriscanolide (2).
Scheme 14: Synthesis of the simplified skeleton of pleuromutilin (1).
Scheme 15: Total synthesis of (−)-nitidasin (93) using a ring-closing metathesis to construct the eight-member...
Scheme 16: Total synthesis of (±)-naupliolide (97).
Scheme 17: Synthesis of the A-B ring structure of fusicoccane (101).
Scheme 18: First attempts of TRCM of dienyne substrates.
Scheme 19: TRCM on optimized substrates towards the synthesis of ophiobolin A (8).
Scheme 20: Tandem ring-closing metathesis for the synthesis of variecolin intermediates 114 and 115.
Scheme 21: Synthesis of poitediol (118) using the allylsilane ring-closing metathesis.
Scheme 22: Access to scaffold 122 by a NHK coupling reaction.
Scheme 23: Key step to construct the [5-8] bicyclooctanone core of aquatolide (4).
Scheme 24: Initial strategy to access aquatolide (4).
Scheme 25: Synthetic plan to cotylenin A (130).
Scheme 26: [5-8] Bicyclic structure of brachialactone (7) constructed by a Mizoroki–Heck reaction.
Scheme 27: Influence of the replacement of the allylic alcohol moiety.
Scheme 28: Formation of variecolin intermediate 140 through a SmI2-mediated Barbier-type reaction.
Scheme 29: SmI2-mediated ketyl addition. Pleuromutilin (1) eight-membered ring closure via C5–C14 bond formati...
Scheme 30: SmI2-mediated dialdehyde cyclization cascade of [5-8-6] pleuromutilin scaffold 149.
Scheme 31: A) Modular synthetic route to mutilin and pleuromutilin family members by Herzon’s group. B) Scaffo...
Scheme 32: Photocatalyzed oxidative ring expansion in pleuromutilin (1) total synthesis.
Scheme 33: Reductive radical cascade cyclization route towards (−)-6-epi-ophiobolin N (168).
Scheme 34: Reductive radical cascade cyclization route towards (+)-6-epi-ophiobolin A (173).
Scheme 35: Radical 8-endo-trig-cyclization of a xanthate precursor.
Figure 5: Structural representations of hypoestin A (177), albolic acid (178), and ceroplastol II (179) beari...
Scheme 36: Synthesis of the common [5-8-5] tricyclic intermediate of hypoestin A (177), albolic acid (178), an...
Scheme 37: Asymmetric synthesis of hypoestin A (177), albolic acid (178), and ceroplastol II (179).
Figure 6: Scope of the Pauson–Khand reaction.
Scheme 38: Nazarov cyclization revealing the fusicoauritone core structure 192.
Scheme 39: Synthesis of fusicoauritone (28) through Nazarov cyclization.
Scheme 40: (+)-Epoxydictymene (5) synthesis through a Nicholas cyclization followed by a Pauson–Khand reaction...
Scheme 41: Synthesis of aquatolide (4) by a Mukaiyama-type aldolisation.
Scheme 42: Tandem Wolff/Cope rearrangement furnishing the A-B bicyclic moiety 204 of variecolin.
Scheme 43: Asymmetric synthesis of the A-B bicyclic core 205 and 206 of variecolin.
Scheme 44: Formation of [5-8]-fused rings by cyclization under thermal activation.
Scheme 45: Construction of the [5-8-6] tricyclic core structure of variecolin (3) by Diels–Alder reaction.
Scheme 46: Synthesis of the [6-4-8-5]-tetracyclic skeleton by palladium-mediated cyclization.
Scheme 47: Access to the [5-8] bicyclic core structure of asteriscanolide (227) through rhodium-catalyzed cycl...
Scheme 48: Total syntheses of asterisca-3(15),6-diene (230) and asteriscanolide (2) with a Rh-catalyzed cycliz...
Scheme 49: Photocyclization of 2-pyridones to access the [5-8-5] backbone of fusicoccanes.
Scheme 50: Total synthesis of (+)-asteriscunolide D (245) and (+)-aquatolide (4) through photocyclization.
Scheme 51: Biocatalysis pathway to construct the [5-8-5] tricyclic scaffold of brassicicenes.
Scheme 52: Influence of the CotB2 mutant over the cyclization’s outcome of GGDP.
Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179
Graphical Abstract
Scheme 1: Organocatalysis classification used in the present perspective.
Scheme 2: Oxidative processes catalyzed by amines.
Scheme 3: N-Heterocyclic carbene (NHC) catalysis in oxidative functionalization of aldehydes.
Scheme 4: Examples of asymmetric oxidative processes catalyzed by chiral Brønsted acids.
Scheme 5: Asymmetric aerobic α-hydroxylation of lactams under phase-transfer organocatalysis conditions emplo...
Scheme 6: Selective CH-oxidation of methylarenes to aldehydes or carboxylic acids.
Scheme 7: An example of the regioselective CH-amination by a sterically hindered imide-N-oxyl radical precurs...
Scheme 8: CH-amination of ethylbenzene and CH-fluorination of aldehydes catalyzed by N-hydroxybenzimidazoles,...
Scheme 9: Mixed hetero-/homogeneous TiO2/N-hydroxyimide photocatalysis in the selective benzylic oxidation.
Scheme 10: Electrochemical benzylic iodination and benzylation of pyridine by benzyl iodides generated in situ...
Scheme 11: Electrochemical oxidative C–O/C–N coupling of alkylarenes with NHPI. Electrolysis conditions: Const...
Scheme 12: Chemoselective alcohol oxidation catalyzed by TEMPO.
Scheme 13: ABNO-catalyzed oxidative C–N coupling of primary alcohols with primary amines.
Scheme 14: ACT-catalyzed electrochemical oxidation of primary alcohols and aldehydes to carboxylic acids.
Scheme 15: Electrocatalytic oxidation of benzylic alcohols by a TEMPO derivative immobilized on a graphite ano...
Scheme 16: Electrochemical oxidation of carbamates of cyclic amines to lactams and oxidative cyanation of amin...
Scheme 17: Hydrogen atom transfer (HAT) and single-electron transfer (SET) as basic principles of amine cation...
Scheme 18: Electrochemical quinuclidine-catalyzed oxidation involving unactivated C–H bonds.
Scheme 19: DABCO-mediated photocatalytic C–C cross-coupling involving aldehyde C–H bond cleavage.
Scheme 20: DABCO-derived cationic catalysts in inactivated C–H bond cleavage for alkyl radical addition to ele...
Scheme 21: Electrochemical diamination and dioxygenation of vinylarenes catalyzed by triarylamines.
Scheme 22: Electrochemical benzylic oxidation mediated by triarylimidazoles.
Scheme 23: Thiyl radical-catalyzed CH-arylation of allylic substrates by aryl cyanides.
Scheme 24: Synthesis of redox-active alkyl tetrafluoropyridinyl sulfides by unactivated C–H bond cleavage by t...
Scheme 25: Main intermediates in quinone oxidative organocatalysis.
Scheme 26: Electrochemical DDQ-catalyzed intramolecular dehydrogenative aryl–aryl coupling.
Scheme 27: DDQ-mediated cross-dehydrogenative C–N coupling of benzylic substrates with azoles.
Scheme 28: Biomimetic o-quinone-catalyzed benzylic alcohol oxidation.
Scheme 29: Electrochemical synthesis of secondary amines by oxidative coupling of primary amines and benzylic ...
Scheme 30: General scheme of dioxirane and oxaziridine oxidative organocatalysis.
Scheme 31: Dioxirane organocatalyzed CH-hydroxylation involving aliphatic C(sp3)–H bonds.
Scheme 32: Enantioselective hydroxylation of CH-acids catalyzed by chiral oxaziridines.
Scheme 33: Iodoarene-organocatalyzed vinylarene diamination.
Scheme 34: Iodoarene-organocatalyzed asymmetric CH-hydroxylation of benzylic substrates.
Scheme 35: Iodoarene-organocatalyzed asymmetric difluorination of alkenes with migration of aryl or methyl gro...
Scheme 36: Examples of 1,2-diiodo-4,5-dimethoxybenzene-catalyzed electrochemical oxidative heterocyclizations.
Scheme 37: Electrochemical N-ammonium ylide-catalyzed CH-oxidation.
Scheme 38: Oxidative dimerization of aryl- and alkenylmagnesium compounds catalyzed by quinonediimines.
Scheme 39: FLP-catalyzed dehydrogenation of N-substituted indolines.
Beilstein J. Org. Chem. 2022, 18, 1062–1069, doi:10.3762/bjoc.18.108
Graphical Abstract
Scheme 1: Strategies for the synthesis of vic-1,2-diols.
Scheme 2: Substrate scope. Reaction conditions: 1 (1.0 mmol), Et4NBr (0.1 equiv), imidazole (0.05 equiv), MeC...
Scheme 3: Investigation of cross-coupling reaction.
Scheme 4: Large-scale experiment.
Scheme 5: Control experiments. aDetermined by 1H NMR using 1,3,5-trimethoxybenzene as an internal standard. b...
Scheme 6: Proposed mechanism.
Beilstein J. Org. Chem. 2022, 18, 588–596, doi:10.3762/bjoc.18.61
Graphical Abstract
Scheme 1: Photochemical transformations of 3-hydroxypyran-4-one derivatives.
Scheme 2: Synthesis and study of the photochemical behavior of compound 16.
Scheme 3: Photoreaction of compound 12a.
Figure 1: 1H NMR monitoring of the photoreaction of compound 12a under UV irradiation (365 nm) in DMSO-d6 sol...
Scheme 4: Proposed mechanism for the photoreaction of compound 11a.
Scheme 5: Synthesis of compounds 15a–l. Reaction conditions: 1) 12a–l (0.5 mmol), AcOH (25 mL), UV irradiatio...
Figure 2: The X-ray crystal structure of compound 15a.
Scheme 6: Synthesis of compounds 15m–o. Reaction conditions: 1) 12m–o (0.5 mmol), AcOH (25 mL), UV irradiatio...
Figure 3: The X-ray crystal structure of compound 15m.
Scheme 7: Synthesis of compound 18.
Figure 4: The X-ray crystal structure of compound 18.
Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53
Graphical Abstract
Figure 1: Molecular structures of (R)-BINOL (left) and (S)-BINOL (right).
Figure 2: Synthesis of Sauvage´s [2]catenanes (S,S)-5 and (S,S)-6 containing two BINOL units by the passive m...
Figure 3: Synthesis of Saito´s [2]rotaxane (R)-10 from a BINOL-based macrocycle by the active metal template ...
Figure 4: Synthesis of Stoddart´s [2]rotaxane (rac)-14 by an ammonium crown ether template.
Figure 5: Synthesis of Stoddart´s BINOL-containing [2]catenanes 18/20/22/24 by π–π recognition.
Figure 6: Synthesis of Takata´s rotaxanes featuring chiral centers on the axle: a) rotaxane (R,R,R/S)-27 obta...
Figure 7: Takata´s chiral polyacetylenes 32/33 featuring BINOL-based [2]rotaxane side chains.
Figure 8: Synthesis of Takata´s chiral thiazolium [2]rotaxanes (R)-35a/b and (R)-38.
Figure 9: Results for the asymmetric benzoin condensation of benzaldehyde (39) with catalysts (R)-35a/b and (R...
Figure 10: Synthesis of Takata´s pyridine-based [2]rotaxane (R)-42.
Figure 11: The asymmetric desymmetrization reaction of meso-1,2-diols with rotaxane (R)-42.
Figure 12: Synthesis of Niemeyer´s axially chiral [2]catenane (S,S)-47.
Figure 13: Results for the enantioselective transfer hydrogenation of 2-phenylquinoline with catalysts (S,S)-47...
Figure 14: Synthesis of Niemeyer´s chiral [2]rotaxanes (S)-56/57.
Figure 15: Results for the enantioselective Michael addition with different rotaxane catalysts (S)-56a/56b/57a/...
Figure 16: Synthesis of Beer´s [2]rotaxanes 64a/b for anion recognition.
Figure 17: Association constants of different anions (used as the Bu4N+ salts) to the [2]rotaxanes (S)-64a/b a...
Figure 18: Synthesis of Beer´s [3]rotaxane (S)-68.
Figure 19: Association constants of different anions (used as the Bu4N+-salts) to the [2]rotaxane (S)-68 and a...
Beilstein J. Org. Chem. 2022, 18, 420–428, doi:10.3762/bjoc.18.44
Graphical Abstract
Scheme 1: Scope of the reaction of bromopropargylic alcohol 1a and phenols 2b–i.
Scheme 2: Reaction of bromopropargylic alcohol 1b and phenols 2a and 2d.
Scheme 3: Reaction of bromopropargylic alcohol 1c and phenol (2a).
Scheme 4: Reaction of chloropropargylic alcohol and phenol (2a).
Scheme 5: Reaction of bromopropargylic alcohol 1a and anilines.
Scheme 6: Control experiments.
Scheme 7: A plausible mechanism for the formation of phenoxyhydroxyketone 4.
Scheme 8: A plausible mechanism for the formation of diphenoxyketone 5.
Scheme 9: Examples of representative preparation of phenoxyketones 4.
Scheme 10: α-Ketol rearrangement of phenoxyketones 4a and 4f.
Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43
Graphical Abstract
Figure 1: Natural bioactive naphthoquinones.
Figure 2: Chemical structures of vitamins K.
Figure 3: Redox cycle of menadione.
Scheme 1: Selected approaches for menadione synthesis using silver(I) as a catalyst.
Scheme 2: Methylation approaches for the preparation of menadione from 1,4-naphthoquinone using tert-butyl hy...
Scheme 3: Methylation approach of 1,4-naphthoquinone using i) rhodium complexes/methylboronic acid and ii) bi...
Scheme 4: Synthesis of menadione (10) from itaconic acid.
Scheme 5: Menadione synthesis via Diels–Alder reaction.
Scheme 6: Synthesis of menadione (10) using p-cresol as a synthetic precursor.
Scheme 7: Synthesis of menadione (10) via demethoxycarbonylating annulation of methyl methacrylate.
Scheme 8: Furan 34 used as a diene in a Diels–Alder reaction for the synthesis of menadione (10).
Scheme 9: o-Toluidine as a dienophile in a Diels–Alder reaction for the synthesis of menadione (10).
Scheme 10: Representation of electrochemical synthesis of menadione.
Figure 4: Reaction sites and reaction types of menadione as substrate.
Scheme 11: DBU-catalyzed epoxidation of menadione (10).
Scheme 12: Phase-transfer catalysis for the epoxidation of menadione.
Scheme 13: Menadione epoxidation using a hydroperoxide derived from (+)-norcamphor.
Scheme 14: Enantioselective Diels–Alder reaction for the synthesis of asymmetric quinone 50 catalyzed by a chi...
Scheme 15: Optimized reaction conditions for the synthesis of anthra[9,1-bc]pyranone.
Scheme 16: Synthesis of anthra[9,1-bc]furanone, anthra[9,1-bc]pyridine, and anthra[9,1-bc]pyrrole derivatives.
Scheme 17: Synthesis of derivatives employing protected trienes.
Scheme 18: Synthesis of cyclobutene derivatives of menadione.
Scheme 19: Menadione reduction reactions using sodium hydrosulfite.
Scheme 20: Green methodology for menadiol synthesis and pegylation.
Scheme 21: Menadione reduction by 5,6-O-isopropylidene-ʟ-ascorbic acid under UV light irradiation.
Scheme 22: Selected approaches of menadione hydroacetylation to diacetylated menadiol.
Scheme 23: Thiele–Winter reaction catalyzed by Bi(OTf)3.
Scheme 24: Carbonyl condensation of menadione using resorcinol and a hydrazone derivative.
Scheme 25: Condensation reaction of menadione with thiosemicarbazide.
Scheme 26: Condensation reaction of menadione with acylhydrazides.
Scheme 27: Menadione derivatives functionalized with organochalcogens.
Scheme 28: Synthesis of selenium-menadione conjugates derived from chloromethylated menadione 84.
Scheme 29: Menadione alkylation by the Kochi–Anderson method.
Scheme 30: Menadione alkylation by diacids.
Scheme 31: Menadione alkylation by heterocycles-substituted carboxylic acids.
Scheme 32: Menadione alkylation by bromoalkyl-substituted carboxylic acids.
Scheme 33: Menadione alkylation by complex carboxylic acids.
Scheme 34: Kochi–Anderson method variations for the menadione alkylation via oxidative decarboxylation of carb...
Scheme 35: Copper-catalyzed menadione alkylation via free radicals.
Scheme 36: Nickel-catalyzed menadione cyanoalkylation.
Scheme 37: Iron-catalyzed alkylation of menadione.
Scheme 38: Selected approaches to menadione alkylation.
Scheme 39: Menadione acylation by photo-Friedel–Crafts acylation reported by Waske and co-workers.
Scheme 40: Menadione acylation by Westwood procedure.
Scheme 41: Synthesis of 3-benzoylmenadione via metal-free TBAI/TBHP system.
Scheme 42: Michael-type addition of amines to menadione reported by Kallmayer.
Scheme 43: Synthesis of amino-menadione derivatives using polyalkylamines.
Scheme 44: Selected examples for the synthesis of different amino-substituted menadione derivatives.
Scheme 45: Selected examples of Michael-type addition of complex amines to menadione (10).
Scheme 46: Addition of different natural α-amino acids to menadione.
Scheme 47: Michael-type addition of amines to menadione using silica-supported perchloric acid.
Scheme 48: Indolylnaphthoquinone or indolylnaphthalene-1,4-diol synthesis reported by Yadav et al.
Scheme 49: Indolylnaphthoquinone synthesis reported by Tanoue and co-workers.
Scheme 50: Indolylnaphthoquinone synthesis from menadione by Escobeto-González and co-workers.
Scheme 51: Synthesis of menadione analogues functionalized with thiols.
Scheme 52: Synthesis of menadione-derived symmetrical derivatives through reaction with dithiols.
Scheme 53: Mercaptoalkyl acids as nucleophiles in Michael-type addition reaction to menadione.
Scheme 54: Reactions of menadione (10) with cysteine derivatives for the synthesis of quinoproteins.
Scheme 55: Synthesis of menadione-glutathione conjugate 152 by Michael-type addition.
Beilstein J. Org. Chem. 2021, 17, 2781–2786, doi:10.3762/bjoc.17.188
Graphical Abstract
Figure 1: (−)-Codonopsinol B (1) and its N-nor-methyl analogue 2; known inhibition activities against α-gluco...
Scheme 1: Synthetic approach towards (±)-codonopsinol B (1) and its N-nor-methyl analogue 2.
Scheme 2: Synthesis of isoxazolidine-4,5-diol (±)-3. Reagents and conditions: (a) ᴅʟ-proline, CHCl3, rt, 48 h...
Scheme 3: Synthesis of final pyrrolidines (±)-1 and (±)-2. Reagents and conditions: (a) vinyl-MgBr, CeCl3, TH...
Figure 2: Molecular structure of N-Cbz-protected pyrrolidine 12 confirmed by single-crystal X-ray crystallogr...