Modern synthetic pathways towards eribulin and its subunits

• Sebastian Dominik Graf

Beilstein J. Org. Chem. 2026, 22, 495–526, doi:10.3762/bjoc.22.37

• metathesis with ethyl acrylate, acidic cleavage of the diol protecting group and addition of NaH induced the oxy-Michael reaction towards 18 in 4:1 dr. Reduction of the ester moiety, subsequent protection with TBDPSCl and methylation of the secondary alcohol furnished 19. After Bn-deprotection, iodination

• –Kishi (NHK) coupling and Pd-mediated cyclization. Fragment 31 was synthesized from known precursor 28 [74] in 9 steps via MMTr-protection, replacement of the Bn- with TBDMS-protecting groups, hydroxylation of sulfone 29 to alcohol 30, tosylation, bromide substitution, acidic MMTr-cleavage and DMP

• . Eventual change of the two PNB- with TBDMS-protecting groups yielded 45 in 58%. Notably, by this technique, the central pyran motif was assembled in one step and required only the stereoinformation of 42`s alcohol unit, while in former works two individual steps and the use of expensive metal catalysts

Recent advances in the stereoselective synthesis of distal biaxially chiral molecules

• Fanxing Zhou,
• Chen Zhang,
• Lingyu Sun,
• Yiyun Fang,
• Siming Zheng,
• Lina Hu,
• Mengyang Shen,
• Zhen Zhao,
• Wei Xu,
• Yunqiang Sun and
• Zi-Qiang Rong

Beilstein J. Org. Chem. 2026, 22, 461–479, doi:10.3762/bjoc.22.34

• -containing five-membered rings with iridium complexes and examined the influence of different alcohol protecting groups on the monoalkyne substrates. The reaction proceeded in generally high yields (>70%) with satisfactory enantioselectivity. Building on this work, Shibata and Tsuchikama developed a one-pot

Synthesis and stereochemical analysis of dynamic planar chiral oxa[7]orthocyclophene

• Yukiho Hashimoto,
• Yuuya Kawasaki,
• Kazunobu Igawa and
• Katsuhiko Tomooka

Beilstein J. Org. Chem. 2026, 22, 436–442, doi:10.3762/bjoc.22.30

• of propargyl alcohol 3 and the alkyne moiety in 3 can be introduced by an alkynylation of the formyl group of aldehyde 4. Thus, we started this synthesis from O-protected 2-bromobenzyl alcohol derivative 5 for the introduction of the propanal moiety of 4 by a Heck reaction with allyl alcohol. The

• synthetic route for the C6-iodo-substituted 1ad is shown in Scheme 2. The Heck reaction of O-TIPS-protected 5a with allyl alcohol in the presence of a palladium catalyst provided the aldehyde 4a in 78% yield [9]. The reaction of 4a with CBr4 and PPh3, followed by treatment with n-BuLi, afforded the terminal

• alkyne 6. Subsequent preparation of the lithium acetylide using n-BuLi, followed by treatment with formaldehyde, afforded propargyl alcohol 3a in 70% yield over three steps. The reaction of 3a with Red-Al generated a vinyl aluminum species, which was then treated with iodine to provide the iodinated Z

Dialkylaminoalkylation of β-ketosulfones via ring-opening of 3-sulfonylpyrrolidines

• Evgeny M. Buev,
• Alexander V. Pavlushin,
• Vladimir S. Moshkin and
• Vyacheslav Y. Sosnovskikh

Beilstein J. Org. Chem. 2026, 22, 383–389, doi:10.3762/bjoc.22.26

• broad spectrum of pharmacological activities [1][2][3] and synthetic potential [4][5]. Also noteworthy are γ-aminosulfones, which form the backbone of important pharmaceuticals including the antiglaucoma drug dorzolamide [6], acamprosate for alcohol craving suppression [7], and bicalutamide, an

• domino-process consists in nucleophilic addition of the alcohol, mercaptan or water (in case the reaction was performed in CH3CN) at the benzoyl group (Scheme 3). The subsequent ring-opening of the pyrrolidine ring can proceed via two possible pathways. First path is the tandem Grob-type fragmentation

• similar process of the reductive elimination of chlorine or chlorosulfonyl groups at the β-position to sulfone [45]. We also examined the starting ammonium salt 3a in the reductive ring-cleavage. As the result, butanamine 5 was formed in 18% yield along with benzylic alcohol. An increase of the reaction

Recent advances in the cleavage of non-activated amides

• Eun-Sol Choi and
• Hyo-Jun Lee

Beilstein J. Org. Chem. 2026, 22, 352–369, doi:10.3762/bjoc.22.23

• introduced at the R1 position (37, 39% yield). The SO2F2-promoted esterification begins with the formation of fluorosulfate K through the reaction of the alcohol with SO2F2. This intermediate then undergoes an SN2 attack by the tautomeric form of amide, generating the iminium species L. In wet solvents (path

• bromine (Br2), which converts the amide into N-bromobenzamide. Meanwhile, at the cathode, the alcohol is partially deprotonated to form an alkoxide, which engages in a stabilizing hydrogen-bonding interaction to produce the acid–base pair V. Nucleophilic attack of V on N-bromobenzamide forms a tetrahedral

• bulky tertiary alcohol 1-adamantanol afforded the ester product 150 in moderate 43% yield. Notably, this esterification protocol is compatible with structurally complex nucleophiles, enabling late-stage modification of drug-derived amides and bioactive OH-containing molecules 153–157. Base-promoted

Synthesis of tricyclic fused pyrrolidine nitroxides from 2-alkynylpyrrolidine-1-oxyls

• Mark M. Gulman,
• Yuliya F. Polienko,
• Sofia Yu. Trakhininа,
• Yuri V. Gatilov,
• Tatyana V. Rybalova,
• Sergey A. Dobrynin and
• Igor A. Kirilyuk

Beilstein J. Org. Chem. 2026, 22, 344–351, doi:10.3762/bjoc.22.22

• group, respectively. The elemental analyses data and high-resolution mass spectra (HRMS) of 6a,b were in agreement with the assigned structure. Oxidation of propargyl alcohols is another way to α,β-acetylenic carbonyl compounds [31]. Mild oxidation of propargyl alcohol 2c with activated manganese

Ring contraction and ring expansion reactions in terpenoid biosynthesis and their application to total synthesis

• Nicolas Kratena,
• Nicolas Heinzig and
• Peter Gärtner

Beilstein J. Org. Chem. 2026, 22, 289–343, doi:10.3762/bjoc.22.21

• alcohol 51b, carbocation 51c is generated and undergoes a 1,2-alkyl shift of the ketone moiety, forming a new bridged 7-membered ring (51d), and completing the skeletal adjustment. A final elimination to the exocyclic olefin delivers the complex, caged structure of anditomin (52). Apart from this D-ring

• shift and aqueous quench of the cation 97b, expanding the 5-membered ring into the allo-cedrane carbon framework, furnishes the proposed biogenetic precursor 97c. Following protonation of the bridgehead alcohol, a Wagner–Meerwein rearrangement, and a 1,2-hydride shift builds up the tricyclo[5.2.1.01,6

• reactive pathway consists of an alkene isomerisation from the propenyl-substituent at C-5, followed by protonation of the C-7 alcohol to give intermediate 116a. From here a transannular cyclopropanation affords the cation 116b, which upon nucleophilic attack of water provides 116c. Expulsion of acetone

A mild and atom-efficient four-component cascade strategy for the construction of biologically relevant 4-hydroxyquinolin-2(1H)-one derivatives

• Dmitrii A. Grishin,
• Kseniia I. Sharkovskaia,
• Ilya G. Kolmakov,
• Daria A. Ipatova,
• Rostislav A. Petrov,
• Nikolai D. Dagaev,
• Dmitry A. Skvortsov,
• Maria G. Khrenova,
• Valeriy V. Andreychev,
• Sergei A. Evteev,
• Yan A. Ivanenkov,
• Roman L. Antipin,
• Olga А. Dontsova and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2026, 22, 244–256, doi:10.3762/bjoc.22.18

• presumably proceed through in situ formation of the Michael acceptor from the condensation of an aromatic aldehyde with Meldrum’s acid, followed by decarboxylation and lactonization to yield the pyranoquinolinedione products (Scheme 1). We hypothesized that employing an alcohol as solvent could induce

• nucleophilic attack by the alcohol on the carbonyl group of the Meldrum’s acid fragment, thereby favoring formation of an open-chain ester rather than a lactone upon decarboxylation. Following this rationale, the reaction of 4-hydroxyquinolin-2-ones 2a–c, 3,4-dimethoxybenzaldehyde, and Meldrum’s acid in

• involving 4-hydroxyquinolinones 2a–c, veratraldehyde, and Meldrum’s acid in alcohol (methanol or ethanol) with ʟ-proline catalysis. Importantly, by employing the alcohol simultaneously as both a reactant and the reaction medium and by fine-tuning the reaction conditions, this cascade can be deliberately

Synthesis of diaryl phosphates using phytic acid as a phosphorus source

• Kazuya Asao,
• Seika Matsumoto,
• Haruka Mori,
• Riku Yoshimura,
• Takeshi Sasaki,
• Naoya Hirata,
• Yasuyuki Hayakawa and
• Shin-ichi Kawaguchi

Beilstein J. Org. Chem. 2026, 22, 213–223, doi:10.3762/bjoc.22.15

• the other mechanism is based on an E2 reaction, which involves the elimination of phosphoric acid accompanied by alkene formation. The phosphoric acid ester of a secondary alcohol releases phosphoric acid and alkenes through thermal degradation, which has been previously observed using isosorbide

• different mechanisms. In addition, the DPpyP 31P NMR peak increases and decreases in conjunction with the decrease of the MPP peak and increase of the DPP peak, suggesting that DPpyP acts as an intermediate in the DPP formation process. When alcohol 1c was used (Figure 3), the reaction stopped mainly at the

Circumventing Mukaiyama oxidation: selective S–O bond formation via sulfenamide–alcohol coupling

• Guoling Huang,
• Huarui Zhu,
• Shuting Zhou,
• Wanlin Zheng,
• Fangpeng Liang,
• Zhibo Zhao,
• Yifei Chen and
• Xunbo Lu

Beilstein J. Org. Chem. 2026, 22, 158–166, doi:10.3762/bjoc.22.9

• previously disclosed a PIDA-mediated oxidative strategy for alcohol incorporation via activation of the S–NH bond (Scheme 1a) [14]. More recently, Wu and co-workers advanced the field by developing a dynamic kinetic resolution protocol for the enantioselective synthesis of sulfinimidate esters from racemic

• , we anticipated that an NBS/NaHCO3-based protocol would provide a more practical and chiral-alcohol-compatible alternative to our previous PIDA system. A conceptual comparison between our previous PIDA-mediated protocol and the present NBS/NaHCO3-mediated protocol is summarized in Scheme 1. However

• lower yields were observed in THF and toluene (Table 1, entries 11 and 12), likely due to poor miscibility or reactivity under the reaction conditions. These findings provide a useful basis for further extending the method to structurally more complex or less soluble alcohol substrates. With the

Total synthesis of natural products based on hydrogenation of aromatic rings

• Haoxiang Wu and
• Xiangbing Qi

Beilstein J. Org. Chem. 2026, 22, 88–122, doi:10.3762/bjoc.22.4

• benzylic alcohol with TFA/Et₃SiH afforded pyridine 95, which underwent a one-pot sequence of indole protection, methylation, and hydrogenation to furnish tetrahydropyridine 96. In contrast to Vollhardt’s synthesis, the unsaturation was misaligned with that of the natural product, most likely arising from

• steps. The authors then utilized their own palladium-catalyzed intramolecular α-acylation followed by protection of the carbonyl group to obtain the diketal 99. Birch reduction of 99 afforded the enone, which was then subjected to a Luche reduction to get the allylic alcohol 100. A Johnson–Claisen

• , constructing the [2.2.2]-bridged ring within the (+)-nominine followed by protection of the primary alcohol as mesylate. Using lithium bromide as the bromine source, an SN2 reaction was performed, and the allylic position was oxidized with tert-butyl peroxide and selenium dioxide to generate the enone 104

Advances in Zr-mediated radical transformations and applications to total synthesis

• Hiroshige Ogawa and
• Hugh Nakamura

Beilstein J. Org. Chem. 2026, 22, 71–87, doi:10.3762/bjoc.22.3

• hydrogen atom from 1,4-cyclohexadiene to furnish the alcohol product. The active species Cp2ZrIII(OTf) is then regenerated via single-electron transfer (SET) from the Ir photocatalyst. Notably, the addition of thiourea 26 significantly improved the regioselectivity in this reaction. According to NMR

• , affording the corresponding alcohol 28. In contrast, when substrates bearing a benzylic alcohol moiety at the α-position were subjected to the same conditions, the reaction proceeded through radical intermediate 31, which underwent a 1,5-hydrogen atom transfer (1,5-HAT) followed by intramolecular C–O bond

• formation to give the cyclic acetal 33. This transformation was applicable to a range of oxetanes 30a–c bearing benzylic alcohol derivatives, each affording the corresponding cyclic acetals in good yields. In 2023, Ota and Yamaguchi et al. reported the hydrogenation of alkyl chlorides via halogen atom

Synthesis and applications of alkenyl chlorides (vinyl chlorides): a review

• Daniel S. Müller

Beilstein J. Org. Chem. 2026, 22, 1–63, doi:10.3762/bjoc.22.1

• oxidation/halogenation reaction of allylic alcohols, as recently reported by Chisholm and co-workers (Scheme 36) [137]. Their approach involves oxidation of the allylic alcohol under Moffatt–Swern conditions, followed by halogenation of the resulting enone to generate a chloronium ion. Subsequent ring

• acidity [145]. This transformation remained unexplored for nearly a decade until Kabalka demonstrated that the benzylic cation could be accessed directly from the corresponding alcohol via its conversion to the benzyloxyboron dichloride (Scheme 42) [146]. Subsequently, Kabalka reported an improved variant

• access cyclohexenyl chlorides via chloride trapping of alkenyl cation intermediates (Scheme 48B) [157]. Comparable yields were obtained when either alkene or alcohol precursors were employed, consistent with the formation of a common cationic intermediate. The method proved limited to six-membered ring

One-pot synthesis of ethylmaltol from maltol

• Immanuel Plangger,
• Marcel Jenny,
• Gregor Plangger and
• Thomas Magauer

Beilstein J. Org. Chem. 2025, 21, 2755–2760, doi:10.3762/bjoc.21.212

• reduction of the newly introduced secondary hydroxy group affords ethylmaltol (1) in four steps overall [1][4]. Different modifications of this approach have been developed, including performing the aldol addition before decarboxylation [5] or using different feedstock chemicals such as furfuryl alcohol

• from corncob to access pyromeconic acid [6]. The second group of synthetic strategies takes advantage of furfural (4), which originates from the acid-catalyzed dehydration of agricultural biomass. It is then converted with an ethyl Grignard compound to alcohol 5 [7]. From alcohol 5, oxidation state

• one-pot conversion of alcohol 5 to ethylmaltol (1) and various patents have focused on this transformation [14][15][16][17][18][19]. While maltol (2) can be obtained through analogous sequences from kojic acid (3) [4][20][21] or furfural (4) [7][9][11][12][13], it is naturally occurring in the leaves

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

• bond formation and functional group compatibility presented unforeseen challenges. Methods for the chemical synthesis of prenyltryptophans (approach A, A–C) are scarce [25][26]. Adopting a bio-inspired approach, Ishikawa et al. treated tryptophan ethyl ester with prenyl alcohol in the presence of 2

• product 11 in 37% yield (Scheme 2). Despite the modest yield, product 11 was transformed to the corresponding tertiary alcohol 12. Removal of the N-Piv group and dehydration with the Burgess reagent [35] led to an inseparable mixture of olefins slightly in favor of the exo-olefin isomer. Dehydration in

Competitive cyclization of ethyl trifluoroacetoacetate and methyl ketones with 1,3-diamino-2-propanol into hydrogenated oxazolo- and pyrimido-condensed pyridones

• Svetlana O. Kushch,
• Marina V. Goryaeva,
• Yanina V. Burgart,
• Marina A. Ezhikova,
• Mikhail I. Kodess,
• Pavel A. Slepukhin,
• Alexandrina S. Volobueva,
• Vladimir V. Zarubaev and
• Victor I. Saloutin

Beilstein J. Org. Chem. 2025, 21, 2716–2729, doi:10.3762/bjoc.21.209

• at the acyl moiety with the amino group of diamino alcohol 3 to generate a three-component intermediate B (Scheme 4). The latter undergoes intramolecular cyclization involving the C=N bond in two equally probable directions: by adding a free amino group to form a hexahydropyrimidine ring of

Tandem hydrothiocyanation/cyclization of CF₃-iminopropargyl alcohols with NaSCN in the presence of AcOH

• Ruslan S. Shulgin,
• Ol’ga G. Volostnykh,
• Anton V. Stepanov,
• Igor’ A. Ushakov,
• Alexander V. Vashchenko and
• Olesya A. Shemyakina

Beilstein J. Org. Chem. 2025, 21, 2694–2702, doi:10.3762/bjoc.21.207

• . Results and Discussion We commenced our investigation using CF3-subsituted iminopropargyl alcohol 1a and NaSCN as model substrates. The completion of the reaction was monitored using IR spectroscopy to observe the disappearance of the band at 2219 cm−1 (–C≡C–). It was found that CF3-iminopropargyl alcohol

• and solvent. In a hexane/H2O biphasic system upon vigorous stirring, the reaction of CF3-iminopropargyl alcohol 1a and the NaSCN/KHSO4 system (ratio of 1a/NaSCN/acid 1:2:2) gave products 2a and 3a in 31% and 10% yields, respectively (Table 1, entry 1). Replacing hexane with THF doubled the yield of

• , providing products 2b,c and 3b,c with similar yields (Table 2, entries 1 and 2). The slightly decreased yield observed for product 3c obtained from iminopropargyl alcohol having a cyclohexyl substituent, is probably due to the steric effect (Table 2, entry 2). The more sterically hindered CF3-iminopropargyl

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

• selectively, and, through acid-catalyzed cyclization, the spiro-E-ring was fused. Elimination of the alcohol moiety at C13 installed the double bond in the correct position at C12–C13. Final Fmoc-deprotection furnished cyclopamine (6). In summary, the Zhu/Gao group disclosed the total synthesis of cyclopamine

• formation and reductive coupling with an aldehyde made accessible β-amino alcohol 60 over two steps. A cascade reaction occurred upon treatment with HCl in acetone followed by treatment with KOH. Indeed, a tandem 5-exo-trig cyclization, sulfinyl removal, and lactamization occurred in one-pot. Finally

• , which provided the need for reprotection of the secondary amine moiety, and the alcohol was eliminated to furnish 65 in three steps. Compound 65 already closely resembles the desired target 12 but lacks the oxidation at C11 and the double bond in position C5–C6. Eight more steps were needed for the

Synthesis of new tetra- and pentacyclic, methylenedioxy- and ethylenedioxy-substituted derivatives of the dibenzo[c,f][1,2]thiazepine ring system

• Gábor Berecz,
• András Dancsó,
• Mária Tóthné Lauritz,
• Loránd Kiss,
• Gyula Simig and
• Balázs Volk

Beilstein J. Org. Chem. 2025, 21, 2645–2656, doi:10.3762/bjoc.21.205

• ): reduction of 8 with NaBH4, followed by chlorination of alcohol 36 with SOCl2 and substitution of chloro derivative 37 with various amines resulted in compounds 38a–c. Tianeptine analogue 38d was obtained by hydrolysis of ester 38c. The synthesis of the new regioisomeric tetracyclic compounds containing the

• regioselectivity. Reduction of 51 with NaBH4 and subsequent chlorination of alcohol 52 with SOCl2 gave chloro derivative 53, which was treated with amines to afford compounds 54a–e. 7-Aminoheptanoic acid ester derivative 54e was hydrolyzed to tianeptine analogue 54f. Conclusion As continuation of our efforts to

Silica gel with covalently attached bambusuril macrocycle for dicyanoaurate sorption from water

• Michaela Šusterová and
• Vladimír Šindelář

Beilstein J. Org. Chem. 2025, 21, 2604–2611, doi:10.3762/bjoc.21.201

• example, an amphiphilic poly(methyl methacrylate)-based polymer modified with calix[4]pyrrole was found to form micelles in water that capture anions from caesium salts and can be precipitated from solution upon heating [11]. Similarly, a hydrogel composed of poly(vinyl alcohol) cross-linked by a “Texas

Visible-light-driven NHC and organophotoredox dual catalysis for the synthesis of carbonyl compounds

• Vasudevan Dhayalan

Beilstein J. Org. Chem. 2025, 21, 2584–2603, doi:10.3762/bjoc.21.200

• –C, C–HA bond-forming reactions [36][37]. These chiral NHC catalysts, used to access enantiopure alcohol/amine derivatives, particularly 2° and 3° alcohols/amines, are significant structural motifs in numerous drugs and natural products and have found widespread synthetic applications in medicinal

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

• , which was subsequently subjected to a one-pot desilylation to afford 24. Reduction of both the ester and ketone functionalities in 24, followed by selective protection of the primary alcohol and re-oxidation of the secondary alcohol to ketone, furnished compound 25 in three steps. The ketone in 25 was

• then converted to vinyl iodide 26 via hydrazine formation followed by iodination using Barton’s method. Subsequent Bouvealt aldehyde synthesis and in situ reduction delivered allylic alcohol 27. Epoxidation of 27 with m-CPBA afforded the rearrangement precursor 28. Protonic acid-promoted semipinacol

• rearrangement of 28 enabled the rearrangement of cis-pentalene to trans-pentalene, delivering intermediate 29, which possesses the same carbon skeleton as the natural product. Further oxidation of the primary alcohol to a carboxylic acid, accompanied by TBS deprotection, afforded hemiketal 30. Finally, a White

Total syntheses of highly oxidative Ryania diterpenoids facilitated by innovations in synthetic strategies

• Zhi-Qi Cao,
• Jin-Bao Qiao and
• Yu-Ming Zhao

Beilstein J. Org. Chem. 2025, 21, 2553–2570, doi:10.3762/bjoc.21.198

• route commenced from (−)-pulegone. After introducing oxidation states at C6 and C10 and installing an alkynyl group at C11, oxidative cleavage of a double bond yielded the key propargylic alcohol intermediate 66. This compound underwent a 1,2-addition with alkynyl Grignard reagent 67, and the resulting

• . Leveraging this regioselective oxidation, the authors achieved the total synthesis of (+)-20-deoxyspiganthine (2) from compound 71. Thus, 71 was converted to 79 via selective SeO2 oxidation (with H2O), triflation, and isopropenyl installation. After protecting the C12 tertiary alcohol and performing a

• , thus establishing the core C and D rings. Base-mediated equilibration fully converted 93 into lactone 94. Finally, selective hydroxy protection in 94, diastereoselective introduction of the C10 secondary alcohol, and global deprotection completed the total synthesis of anhydroryanodol (10). Application

Ni-promoted reductive cyclization cascade enables a total synthesis of (+)-aglacin B

• Si-Chen Yao,
• Jing-Si Cao,
• Jian Xiao,
• Ya-Wen Wang and
• Yu Peng

Beilstein J. Org. Chem. 2025, 21, 2548–2552, doi:10.3762/bjoc.21.197

• cyclization, and a subsequent acetal reduction under acidic conditions then can complete the total synthesis of this molecule. The cyclization precursor 5 could be prepared from the primary alcohol 6 through transforming functional groups of the alkyl chain and installing an allyl group. It was envisioned

• diastereocontrol for 12 (dr = 20:1), and could easily proceed on a scale of ten grams (Supporting Information File 1). For the reduction of the chiral auxiliary in 12, NaBH4 in THF/H2O proved to be the optimal conditions, giving the primary alcohol 6 in 80% yield. Subsequently, oxidation of this alcohol by IBX

• 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCD) in CH2Cl2 followed by reaction with allyl alcohol, provided β-bromo acetal 5 in 30% overall yield starting from alcohol 6. With a successful preparation of the cyclization precursor 5, the designed nickel-promoted reductive tandem cyclization was pursued

Rapid access to the core of malayamycin A by intramolecular dipolar cycloaddition

• Yilin Liu,
• Yuchen Yang,
• Chen Yang,
• Sha-Hua Huang,
• Jian Jin and
• Ran Hong

Beilstein J. Org. Chem. 2025, 21, 2542–2547, doi:10.3762/bjoc.21.196

• details). The following reductive cleavage of the N–O bond was carried out by Mo(CO)6 in refluxing CH3CN [39]. Subsequent oxidation of the resulting secondary alcohol with Dess–Martin periodinane (DMP) [40] afforded methyl ketone 20 in 53% yield for 2 steps. Moreover, the minor isomer 19b also underwent

• from the INOC cycloaddition can be converted to a single stereoisomer of 20. With all required stereogenic centers embedded in the 6-5 trans-fused bicyclic skeleton, the remaining problem is converting C to O to install the secondary alcohol at C2 with retention of the β-configuration. The programmed