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Recent advancements in the synthesis of Veratrum alkaloids
- Morwenna Mögel,
- David Berger and
- Philipp Heretsch
Beilstein J. Org. Chem. 2025, 21, 2657–2693, doi:10.3762/bjoc.21.206
Graphical Abstract
Scheme 1: Representatives of steroid alkaloid classes. Marked in blue is the steroidal cholestane framework, ...
Scheme 2: Subclasses of Veratrum alkaloids: jervanine, veratramine and cevanine-type [8].
Scheme 3: Flow chart presentation of the synthesis of (−)-englerin A developed by the Christmann group [10].
Scheme 4: Structures and year of synthesis of the three types of Veratrum alkaloids reported in the literatur...
Scheme 5: Key step in the synthesis of cyclopamine (6) by the Giannis group [21].
Scheme 6: Overview of the semisynthesis of cyclopamine (6) reported by the Giannis group in 2009 [21].
Scheme 7: Key steps in the synthesis of cyclopamine (6) by the Baran group [23].
Scheme 8: Overview of the total synthesis of cyclopamine (6) by the Baran group in 2023 [23].
Scheme 9: Key steps in the synthesis of cyclopamine (6) by the Zhu/Gao group [25].
Scheme 10: Overview of the total synthesis of cyclopamine (6) by the group of Zhao/Gao in 2023 [25].
Scheme 11: Key steps in the synthesis of cyclopamine (6) by the Liu/Qin group [26].
Scheme 12: Overview of the semisynthesis of cyclopamine (6) by the Liu/Qin group in 2024 [26].
Scheme 13: Key steps in the synthesis of jervine (12) by the Masamune group [14].
Scheme 14: Overview of the total synthesis of jervine (12) by the Masamune group in 1968 [14].
Scheme 15: Color-coded schemes of the presented cyclopamine (6) syntheses by Giannis, Baran, Zhu/Gao, and Liu/...
Scheme 16: Key steps in the total synthesis of veratramine (13) by the Johnson group [15].
Scheme 17: Overview of the total synthesis of veratramine (13) by the Johnson group in 1967 [15].
Scheme 18: Key steps in the synthesis of veratramine (13) by the Zhu/Gao group [25].
Scheme 19: Shortened overview of the total synthesis of veratramine (13) by the Zhu/Gao group in 2023 [25].
Scheme 20: Key steps in the synthesis of veratramine by the Liu/Qin group [26].
Scheme 21: Overview of the semisynthesis of veratramine (13) by the Liu/Qin group in 2024 [26].
Scheme 22: Key steps in the synthesis of veratramine (13) by the Trauner group [27].
Scheme 23: Overview of the total synthesis of veratramine (13) by the Trauner group in 2025 [27].
Scheme 24: Key steps in the synthesis of verarine (14) by the Kutney group [16-19].
Scheme 25: Overview of the total synthesis of verarine (14) by the Kutney group reported 1962–1968 [16-19].
Scheme 26: Color-coded schemes of the presented veratramine-type alkaloid synthesis of Zhu/Gao, Liu/Qin and Tr...
Scheme 27: Structures of veracevine (86), veratridine (87), and cevadine (88).
Scheme 28: Key step in the semisynthesis of verticine (15) by the Kutney group (1977) [20,46].
Scheme 29: Overview of the semisynthesis of verticine (15) by the Kutney group (1977) [20,46].
Scheme 30: Key step of the total synthesis of (±)-4-methylenegermine (17) by the Stork group (2017) [22].
Scheme 31: Overview of the total synthesis of (±)-4-methylenegermine (17) by the Stork group (2017) [22].
Scheme 32: Key step of the total synthesis of heilonine (16) by Cassaidy and Rawal (2021) [24].
Scheme 33: Overview of the total synthesis of heilonine (16) by Cassaidy and Rawal (2021) [24]. FGI: functional gr...
Scheme 34: Key steps of the synthesis of heilonine (16) by Dai and co-workers (2024) [28].
Scheme 35: Overview of the total synthesis of heilonine (16) by Dai and co-workers (2024) [28].
Scheme 36: Key steps of the total synthesis of zygadenine (18) reported by Luo and co-workers [29].
Scheme 37: Overview of the total synthesis of zygadenine (18) by Luo and co-workers (2023) [29].
Scheme 38: Key step of the divergent total syntheses of highly oxidized cevanine-type alkaloids by Luo and co-...
Scheme 39: Divergent syntheses of highly oxidized cevanine-type alkaloids by Luo and co-workers (2024) [30].
Scheme 40: Color-coded overview of the presented cevanine-type alkaloid syntheses [10,20,22,24,28-30,46]. LLS: longest linear sequen...
New tandem Ugi/intramolecular Diels–Alder reaction based on vinylfuran and 1,3-butadienylfuran derivatives
- Yuriy I. Horak,
- Roman Z. Lytvyn,
- Andrii R. Vakhula,
- Yuriy V. Homza,
- Nazariy T. Pokhodylo and
- Mykola D. Obushak
Beilstein J. Org. Chem. 2025, 21, 444–450, doi:10.3762/bjoc.21.31
Graphical Abstract
Figure 1: State of the art of Ugi/Diels–Alder reaction based on furan.
Scheme 1: Preparation of 4,4a,5,6,7,7a-hexahydro-3aH-furo[2,3-f]isoindoles via Ugi/IMDAV tandem reaction.
Scheme 2: Kinetic product 5 does not transform into thermodynamic product 6.
Scheme 3: Synthesis of compounds 6a.
Scheme 4: Synthesis of compound 7.
Scheme 5: Synthesis of compounds 9.
Photoswitches beyond azobenzene: a beginner’s guide
- Michela Marcon,
- Christoph Haag and
- Burkhard König
Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143
Graphical Abstract
Figure 1: Energy diagram of a two-state photoswitch. Figure 1 was redrawn from [2].
Figure 2: Example of the absorption spectra of the isomers of a photoswitch with most efficient irradiation w...
Scheme 1: Photoswitch classes described in this review.
Figure 3: Azoheteroarenes.
Scheme 2: E–Z Isomerisation (top) and mechanisms of thermal Z–E isomerisation (bottom).
Scheme 3: Rotation mechanism favoured by the electron displacement in push–pull systems. Selected examples of...
Figure 4: A) T-shaped and twisted Z-isomers determine the thermal stability and the Z–E-PSS (selected example...
Figure 5: Effect of di-ortho-substitution on thermal half-life and PSS.
Figure 6: Selected thermal lifetimes of azoindoles in different solvents and concentrations. aConcentration o...
Figure 7: Aryliminopyrazoles: N-pyrazoles (top) and N-phenyl (bottom).
Scheme 4: Synthesis of symmetrical heteroarenes through oxidation (A), reduction (B), and the Bayer–Mills rea...
Scheme 5: Synthesis of diazonium salt (A); different strategies of azo-coupling: with a nucleophilic ring (B)...
Scheme 6: Synthesis of arylazothiazoles 25 (A) and heteroaryltriazoles 28 (B).
Scheme 7: Synthesis of heteroarylimines 31a,b [36-38].
Figure 8: Push–pull non-ionic azo dye developed by Velasco and co-workers [45].
Scheme 8: Azopyridine reported by Herges and co-workers [46].
Scheme 9: Photoinduced phase transitioning azobispyrazoles [47].
Figure 9: Diazocines.
Scheme 10: Isomers, conformers and enantiomers of diazocine.
Scheme 11: Partial overlap of the ππ* band with electron-donating substituents and effect on the PSS. Scheme 11 was ada...
Figure 10: Main properties of diazocines with different bridges. aMeasured in n-hexane [56]. bMeasured in THF. cMe...
Scheme 12: Synthesis of symmetric diazocines.
Scheme 13: Synthesis of asymmetric diazocines.
Scheme 14: Synthesis of O- and S-heterodiazocines.
Scheme 15: Synthesis of N-heterodiazocines.
Scheme 16: Puromycin diazocine photoswitch [60].
Figure 11: Indigoids.
Figure 12: The main representatives of the indigoid photoswitch class.
Scheme 17: Deactivation process that prevents Z-isomerisation of indigo.
Figure 13: Stable Z-indigo derivative synthesised by Wyman and Zenhäusern [67].
Figure 14: Selected examples of indigos with aliphatic and aromatic substituents [68]. Dashed box: proposed π–π in...
Scheme 18: Resonance structures of indigo and thioindigo involving the phenyl ring.
Scheme 19: Possible deactivation mechanism for 4,4'-dihydroxythioindigo [76].
Scheme 20: Effect of different heteroaryl rings on the stability and the photophysical properties of hemiindig...
Figure 15: Thermal half-lives of red-shifted hemithioindigos in toluene [79]. aMeasured in toluene-d8.
Scheme 21: Structures of pyrrole [81] and imidazole hemithioindigo [64].
Figure 16: Examples of fully substituted double bond hemithioindigo (left), oxidised hemithioindigos (centre),...
Scheme 22: Structure of iminothioindoxyl 72 (top) and acylated phenyliminoindolinone photoswitch 73 (bottom). ...
Scheme 23: (top) Transition states of iminothioindoxyl 72. The planar transition state is associated with a lo...
Scheme 24: Baeyer–Drewsen synthesis of indigo (top) and N-functionalisation strategies (bottom).
Scheme 25: Synthesis of hemiindigo.
Scheme 26: Synthesis of hemithioindigo and iminothioindoxyl.
Scheme 27: Synthesis of double-bond-substituted hemithioindigos.
Scheme 28: Synthesis of phenyliminoindolinone.
Scheme 29: Hemithioindigo molecular motor [85].
Figure 17: Arylhydrazones.
Scheme 30: Switching of arylhydrazones. Note: The definitions of stator and rotor are arbitrary.
Scheme 31: Photo- and acidochromism of pyridine-based phenylhydrazones.
Scheme 32: A) E–Z thermal inversion of a thermally stable push–pull hydrazone [109]. B) Rotation mechanism favoured...
Scheme 33: Effect of planarisation on the half-life.
Scheme 34: The longest thermally stable hydrazone switches reported so far (left). Modulation of thermal half-...
Figure 18: Dependency of t1/2 on concentration and hypothesised aggregation-induced isomerisation.
Figure 19: Structure–property relationship of acylhydrazones.
Scheme 35: Synthesis of arylhydrazones.
Scheme 36: Synthesis of acylhydrazones.
Scheme 37: Photoswitchable fluorophore by Aprahamian et al. [115].
Scheme 38: The four-state photoswitch synthesised by the Cigáň group [116].
Figure 20: Diarylethenes.
Scheme 39: Isomerisation and oxidation pathway of E-stilbene to phenanthrene.
Scheme 40: Strategies adapted to avoid E–Z isomerisation and oxidation.
Scheme 41: Molecular orbitals and mechanism of electrocyclisation for a 6π system.
Figure 21: Aromatic stabilisation energy correlated with the thermal stability of the diarylethenes [127,129].
Figure 22: Half-lives of diarylethenes with increasing electron-withdrawing groups [128,129].
Scheme 42: Photochemical degradation pathway promoted by electron-donating groups [130].
Figure 23: The diarylethenes studied by Hanazawa et al. [134]. Increased rigidity leads to bathochromic shift.
Scheme 43: The dithienylethene synthesised by Nakatani's group [135].
Scheme 44: Synthesis of perfluoroalkylated diarylethenes.
Scheme 45: Synthesis of 139 and 142 via McMurry coupling.
Scheme 46: Synthesis of symmetrical derivatives 145 via Suzuki–Miyaura coupling.
Scheme 47: Synthesis of acyclic 148, malonic anhydride 149, and maleimide derivatives 154.
Figure 24: Gramicidin S (top left) and two of the modified diarylethene derivatives: first generation (bottom ...
Scheme 48: Pyridoxal 5'-phosphate and its reaction with an amino acid (top). The analogous dithienylethene der...
Figure 25: Fulgides.
Scheme 49: The three isomers of fulgides.
Scheme 50: Thermal and photochemical side products of unsubstituted fulgide [150].
Figure 26: Maximum absorption λc of the closed isomer compared with the nature of the aromatic ring and the su...
Scheme 51: Possible rearrangement of the excited state of 5-dimethylaminoindolylfulgide [153].
Figure 27: Quantum yields of ring closure (ΦE→C) and E–Z isomerisation (ΦE→Z) correlated with the increasing s...
Scheme 52: Active (Eα) and inactive (Eβ) conformers (left) and the bicyclic sterically blocked fulgide 169 (ri...
Scheme 53: Quantum yield of ring-opening (ΦC→E) and E–Z isomerisation (ΦE→Z) for different substitution patter...
Scheme 54: Stobbe condensation pathway for the synthesis of fulgides 179, fulgimides 181 and fulgenates 178.
Scheme 55: Alternative synthesis of fulgides through Pd-catalysed carbonylation.
Scheme 56: Optimised synthesis of fulgimides [166].
Scheme 57: Photoswitchable FRET with a fulgimide photoswitch [167].
Scheme 58: Three-state fulgimide strategy by Slanina's group.
Figure 28: Spiropyrans.
Scheme 59: Photochemical (left) and thermal (right) ring-opening mechanisms for an exemplary spiropyran with a...
Figure 29: Eight possible isomers of the open merocyanine according to the E/Z configurations of the bonds hig...
Scheme 60: pH-Controlled photoisomerisation between the closed spiropyran 191-SP and the open E-merocyanine 19...
Scheme 61: Behaviour of spiropyran in water buffer according to Andréasson and co-workers [180]. 192-SP in an aqueo...
Scheme 62: (left box) Proposed mechanism of basic hydrolysis of MC [184]. (right box) Introduction of electron-dona...
Scheme 63: Photochemical interconversion of naphthopyran 194 (top) and spirooxazine 195 (bottom) photoswitches...
Scheme 64: Synthesis of spiropyrans and spirooxazines 198 and the dicondensation by-product 199.
Scheme 65: Alternative synthesis of spiropyrans and spirooxazines with indolenylium salt 200.
Scheme 66: Synthesis of 4’-substituted spiropyrans 203 by condensation of an acylated methylene indoline 201 w...
Scheme 67: Synthesis of spironaphthopyrans 210 by acid-catalysed condensation of naphthols and diarylpropargyl...
Scheme 68: Photoswitchable surface wettability [194].
Figure 30: Some guiding principles for the choice of the most suitable photoswitch. Note that this guide is ve...
Photocatalysis and photochemistry in organic synthesis
- Timothy Noël and
- Bartholomäus Pieber
Beilstein J. Org. Chem. 2025, 21, 1645–1647, doi:10.3762/bjoc.21.128
Recent advances in total synthesis of illisimonin A
- Juan Huang and
- Ming Yang
Beilstein J. Org. Chem. 2025, 21, 2571–2583, doi:10.3762/bjoc.21.199
Graphical Abstract
Figure 1: The categorization of Illicium sesquiterpenes and representative natural products.
Figure 2: The original assigned (−)-illisimonin A, revised (−)-illisimonin A, and their different draws.
Scheme 1: Proposed biosynthetic pathway of illisimonin A by Yu et al.
Scheme 2: Rychnovsky’s racemic synthesis of illisimonin A (1).
Scheme 3: The absolute configuration revision of (−)-illisimonin A.
Scheme 4: Kalesse’s asymmetric synthesis of (−)-illisimonin A.
Scheme 5: Yang group proposed biosynthetic pathway of illisimonin A.
Scheme 6: Yang’s bioinspired synthesis of illisimonin A.
Scheme 7: Dai’s asymmetric synthesis of (–)-illisimonin A.
Scheme 8: Lu’s total synthesis of illisimonin A.
Scheme 9: Initial efforts toward the total synthesis of illisimonin A by the Lu Group.
Scheme 10: Suzuki’s synthetic effort towards illisimonin A.
Total synthesis of asperdinones B, C, D, E and terezine D
- Ravi Devarajappa and
- Stephen Hanessian
Beilstein J. Org. Chem. 2025, 21, 2730–2738, doi:10.3762/bjoc.21.210
Graphical Abstract
Figure 1: Structures of prenylindole alkaloids derived from tryptophan.
Figure 2: Representative retrosynthetic considerations for 7-prenyl- and 7-allyltryptophan.
Scheme 1: C-7 Functionalization of 7-iodo-Nα-Boc-tryptophan methyl ester.
Scheme 2: C-7 Prenylation via C–H activation.
Figure 3: Negishi cross-coupling of allyl- and prenyl(iodo)indoles.
Scheme 3: Synthesis of prenyl- and allylindoles.
Scheme 4: Markovnikov hydrochlorination and hydrotrifluoroacetylation.
Scheme 5: Synthesis of asperdinones B–E 1–4.
Scheme 6: Control experiment.
Scheme 7: Control experiment of the Negishi cross-coupling reaction.
Scheme 8: Synthesis of terezine D and ent-asperdinone E.
Chiral phosphoric acid-catalyzed asymmetric synthesis of helically chiral, planarly chiral and inherently chiral molecules
- Wei Liu and
- Xiaoyu Yang
Beilstein J. Org. Chem. 2025, 21, 1864–1889, doi:10.3762/bjoc.21.145
Graphical Abstract
Figure 1: General structure of CPAs and selected CPAs with various chiral scaffolds.
Figure 2: Representative elements of molecular chirality.
Scheme 1: CPA-catalyzed asymmetric synthesis of azahelicenes via Fischer indole synthesis.
Scheme 2: CPA-catalyzed asymmetric synthesis of azahelicenes via sequential Povarov reaction and oxidative ar...
Scheme 3: CPA-catalyzed asymmetric synthesis of azahelicenes via sequential Povarov reaction involving 3-viny...
Scheme 4: CPA-catalyzed asymmetric synthesis of heterohelicenes via sequential Povarov reaction involving 2-v...
Scheme 5: Diverse enantioselective synthesis of hetero[7]helicenes via a CPA-catalyzed double annulation stra...
Scheme 6: CPA-catalyzed asymmetric synthesis of indolohelicenoids through enantioselective cycloaddition and ...
Scheme 7: Kinetic resolution of helical polycyclic phenols via CPA-catalyzed enantioselective aminative dearo...
Scheme 8: Kinetic resolution of azahelicenes via CPA-catalyzed transfer hydrogenation.
Scheme 9: Asymmetric synthesis of planarly chiral macrocycles via CPA-catalyzed electrophilic aromatic aminat...
Scheme 10: Enantioselective synthesis of planarly chiral macrocycles via CPA-catalyzed macrocyclization.
Scheme 11: (Dynamic) kinetic resolution of planarly chiral paracyclophanes via CPA-catalyzed asymmetric reduct...
Scheme 12: Kinetic resolution of macrocyclic paracyclophanes through CPA/Bi-catalyzed asymmetric allylation.
Scheme 13: Enantioselective synthesis of planarly chiral macrocycles via CPA-catalyzed coupling of carboxylic ...
Scheme 14: Kinetic resolution of substituted amido[2.2]paracyclophanes via CPA-catalyzed asymmetric electrophi...
Scheme 15: Enantioselective synthesis of inherently chiral calix[4]arenes via sequential CPA-catalyzed Povarov...
Scheme 16: Asymmetric synthesis of inherently chiral calix[4]arenes via CPA-catalyzed aminative desymmetrizati...
Scheme 17: Asymmetric synthesis of chiral heterocalix[4]arenes via CPA-catalyzed intramolecular SNAr reaction.
Scheme 18: Enantioselective synthesis of inherently chiral DDDs via CPA-catalyzed cyclocondensation.
Scheme 19: Asymmetric synthesis of saddle-shaped inherently chiral 9,10-dihydrotribenzoazocines via CPA-cataly...
Scheme 20: Enantioselective synthesis of inherently chiral saddle-shaped dibenzo[b,f][1,5]diazocines via CPA-c...
Scheme 21: Enantioselective synthesis of inherent chiral 7-membered tribenzocycloheptene oximes via CPA-cataly...
Synthetic applications of the Cannizzaro reaction
- Bhaskar Chatterjee,
- Dhananjoy Mondal and
- Smritilekha Bera
Beilstein J. Org. Chem. 2024, 20, 1376–1395, doi:10.3762/bjoc.20.120
Graphical Abstract
Figure 1: Types and mechanism of the Cannizzaro reaction.
Figure 2: Various approaches of the Cannizzaro reaction.
Figure 3: Representative molecules synthesized via the Cannizzaro reaction.
Scheme 1: Intramolecular Cannizzaro reaction of aryl glyoxal hydrates using TOX catalysts.
Scheme 2: Intramolecular Cannizzaro reaction of aryl methyl ketones using ytterbium triflate/selenium dioxide....
Scheme 3: Intramolecular Cannizzaro reaction of aryl glyoxals using Cr(ClO4)3 as catalyst.
Scheme 4: Cu(II)-PhBox-catalyzed asymmetric Cannizzaro reaction.
Scheme 5: FeCl3-based chiral catalyst applied for the enantioselective intramolecular Cannizzaro reaction rep...
Scheme 6: Copper bis-oxazoline-catalysed intramolecular Cannizzaro reaction and proposed mechanism.
Scheme 7: Chiral Fe catalysts-mediated enantioselective Cannizzaro reaction.
Scheme 8: Ruthenium-catalyzed Cannizzaro reaction of aromatic aldehydes.
Scheme 9: MgBr2·Et2O-assisted Cannizzaro reaction of aldehydes.
Scheme 10: LiBr-catalyzed intermolecular Cannizzaro reaction of aldehydes.
Scheme 11: γ-Alumina as a catalyst in the Cannizzaro reaction.
Scheme 12: AlCl3-mediated Cannizzaro disproportionation of aldehydes.
Scheme 13: Ru–N-heterocyclic carbene catalyzed dehydrogenative synthesis of carboxylic acids.
Figure 4: Proposed catalytic cycle for the dehydrogenation of alcohols.
Scheme 14: Intramolecular desymmetrization of tetraethylene glycol.
Scheme 15: Desymmetrization of oligoethylene glycol dialdehydes.
Scheme 16: Intramolecular Cannizzaro reaction of calix[4]arene dialdehydes.
Scheme 17: Desymmetrization of dialdehydes of symmetrical crown ethers using Ba(OH)2.
Scheme 18: Synthesis of ottelione A (proposed) via intramolecular Cannizzaro reaction.
Scheme 19: Intramolecular Cannizzaro reaction for the synthesis of pestalalactone.
Scheme 20: Synthetic strategy towards nigricanin involving an intramolecular Cannizzaro reaction.
Scheme 21: Spiro-β-lactone-γ-lactam part of oxazolomycins via aldol crossed-Cannizzaro reaction.
Scheme 22: Synthesis of indole alkaloids via aldol crossed-Cannizzaro reaction.
Scheme 23: Aldol and crossed-Cannizzaro reaction towards the synthesis of ertuliflozin.
Scheme 24: Synthesis of cyclooctadieneones using a Cannizzaro reaction.
Scheme 25: Microwave-assisted crossed-Cannizzaro reaction for the synthesis of 3,3-disubstituted oxindoles.
Scheme 26: Synthesis of porphyrin-based rings using the Cannizzaro reaction.
Scheme 27: Synthesis of phthalides and pestalalactone via Cannizarro–Tishchenko-type reaction.
Scheme 28: Synthesis of dibenzoheptalene bislactones via a double intramolecular Cannizzaro reaction.
Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters
- Carlos R. Azpilcueta-Nicolas and
- Jean-Philip Lumb
Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35
Graphical Abstract
Scheme 1: Comparison between Barton and NHPI ester radical precursors.
Scheme 2: Overview of the mechanisms and activation modes involved in radical generation from RAEs.
Scheme 3: Common mechanisms in photocatalysis.
Scheme 4: A) Giese-type radical addition of NHPI esters mediated by a reductive quenching photocatalytic cycl...
Scheme 5: A) Minisci-type radical addition of NHPI esters. B) Reaction mechanism involving an “off-cycle” red...
Scheme 6: Activation of NHPI esters through hydrogen-bonding in an oxidative quenching photocatalytic cycle.
Scheme 7: SET activation of RAE facilitated by a Lewis acid catalyst.
Scheme 8: PCET activation of NHPI esters in the context of a radical-redox annulation.
Scheme 9: Activation enabled by a strong excited-state reductant catalyst and its application in the dearomat...
Scheme 10: Proposed formation of an intramolecular charge-transfer complex in the synthesis of (spiro)anellate...
Scheme 11: Formation of a charge-transfer complex between enamides and NHPI esters enabled by a chiral phospha...
Scheme 12: Activation of NHPI ester through the formation of photoactive EDA-complexes.
Scheme 13: A) EDA complex-mediated radical hydroalkylation reactions of NHPI esters. B) Proposed mechanism for...
Scheme 14: Proposed radical chain mechanism initiated by EDA-complex formation.
Scheme 15: A) Photoinduced decarboxylative borylation. B) Proposed radical chain mechanism.
Scheme 16: A) Activation of NHPI esters mediated by PPh3/NaI. B) Proposed catalytic cycle involving EDA-comple...
Scheme 17: A) Radical generation facilitated by EDA complex formation between PTH1 catalyst and NHPI esters. B...
Scheme 18: Proposed catalytic cycle for the difunctionalization of styrenes.
Scheme 19: Formation of a charge-transfer complex between NHPI esters and Cs2CO3 enables decarboxylative amina...
Scheme 20: 3-Acetoxyquinuclidine as catalytic donor in the activation of TCNHPI esters.
Scheme 21: A) Photoinduced Cu-catalyzed decarboxylative amination. B) Proposed catalytic cycle. C) Radical clo...
Scheme 22: A) Photoinduced Pd-catalyzed aminoalkylation of 1,4-dienes. B) Proposed catalytic cycle.
Scheme 23: A) TM-catalyzed decarboxylative coupling of NHPI esters and organometallic reagents. B) Representat...
Scheme 24: Synthetic applications of the TM-catalyzed decarboxylative coupling of NHPI esters and organometall...
Scheme 25: A) Ni-catalyzed cross-electrophile coupling of NHPI esters. B) Representative catalytic cycle.
Scheme 26: A) Synthetic applications of decarboxylative cross-electrophile couplings. B) Decarboxylative aryla...
Scheme 27: A) Activation of tetrachlorophthalimide redox-active esters enabled by a low-valency Bi complex. B)...
Scheme 28: Activation of NHPI esters mediated by Zn0 applied in a Z-selective alkenylation reaction.
Scheme 29: A) Activation of NHPI esters enabled by a pyridine-boryl radical species applied to the decarboxyla...
Scheme 30: A) Decarboxylative coupling of RAE and aldehydes enabled by NHC-catalyzed radical relay. B) Propose...
Scheme 31: A) Decarboxylative C(sp3)–heteroatom coupling reaction of NHPI esters under NHC catalysis B) The NH...
Scheme 32: A) Electrochemical Giese-type radical addition of NHPI esters. B) Reaction mechanism.
Scheme 33: Electrochemical Minisci-type radical addition of NHPI-esters.
Scheme 34: Ni-electrocatalytic cross-electrophile coupling of NHPI esters with aryl iodides.
Scheme 35: A) Decarboxylative arylation of NHPI esters under Ag-Ni electrocatalysis B) Formation of AgNP on th...
Scheme 36: Synthetic applications of decarboxylative couplings of NHPI esters under Ni-electrocatalysis.
Scheme 37: Examples of natural product syntheses in which RAEs were used in key C–C bond forming reactions.
Chemoenzymatic synthesis of the cardenolide rhodexin A and its aglycone sarmentogenin
- Fuzhen Song,
- Mengmeng Zheng,
- Dongkai Wang,
- Xudong Qu and
- Qianghui Zhou
Beilstein J. Org. Chem. 2025, 21, 2637–2644, doi:10.3762/bjoc.21.204
Graphical Abstract
Figure 1: Representative CGs with promising biological activities.
Scheme 1: Retrosynthetic analysis of rhodexin A and sarmentogenin.
Scheme 2: Chemoenzymatic synthesis of sarmentogenin (2).
Scheme 3: Synthesis of rhodexin A.
