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Search for "hydrolysis" in Full Text gives 919 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Recent advances in total synthesis of illisimonin A
Beilstein J. Org. Chem. 2025, 21, 2571–2583, doi:10.3762/bjoc.21.199
- triflate formation followed by a palladium-catalyzed coupling reaction with AlMe3. The carbonyl group at C8, required for the subsequent aldol reaction, was introduced by enolate oxidation followed by Jones oxidation. Hydrolysis of the ketal at C11 afforded ketoester 64. A TBD (1,5,7-triazabicyclo[4.4.0
- ). Chemoselective epoxidation of the enone double bond in 69 yielded epoxide 70. A Wittig reaction of 70 with (methoxymethyl)triphenylphosphonium chloride and t-BuOK generated a methyl enol ether, which was unstable in the presence of the epoxide. During aqueous workup, simultaneous hydrolysis of the enol ether and
- intramolecular Diels–Alder reaction, affording 102 and 103 in 91% yield with a 1:6 ratio. The major product 103 was selected to investigate the tandem retro-Claisen/aldol reaction. Hydrolysis of the enol methyl ether in 103 under acidic conditions delivered triketone 104. Subsequent treatment of 104 with aqueous
Total syntheses of highly oxidative Ryania diterpenoids facilitated by innovations in synthetic strategies
Beilstein J. Org. Chem. 2025, 21, 2553–2570, doi:10.3762/bjoc.21.198
- limitations in technical capabilities at the time, its absolute configuration remained undetermined. Over the subsequent two decades, its hydrolysis product ryanodol (4) and several structurally related analogs were isolated sequentially [9][10][11][12][13][14]. The absolute configurations of both 1 and 4
- the correct relative configuration undergoes hydrolysis of its spirocyclic lactone moiety under basic conditions to yield 13, establishing the critical C5 chiral center. Under acidic conditions, intermediate 13 undergoes ketal deprotection followed by successive intramolecular aldol reactions
- compound 19. This intermediate is converted to lactone 20 via base-promoted Grob fragmentation followed by acid-mediated MOM deprotection. Epoxidation of the C10–C11 double bond in 20, lactone hydrolysis-promoted epoxide ring opening, and inversion of the C10 hydroxy configuration, yield the key
Rapid access to the core of malayamycin A by intramolecular dipolar cycloaddition
Beilstein J. Org. Chem. 2025, 21, 2542–2547, doi:10.3762/bjoc.21.196
- from the use of crotyl bromide as a mixture of geometric isomers. After installation of the crotyl group, hydrolysis of the acetonide group and oxidative cleavage of diol 16, oxime 17 was prepared through the condensation of the aldehyde with hydroxylamine in overall 59% yield. Upon oxidation with
Isoorotamide-based peptide nucleic acid nucleobases with extended linkers aimed at distal base recognition of adenosine in double helical RNA
Beilstein J. Org. Chem. 2025, 21, 2513–2523, doi:10.3762/bjoc.21.193
- % of the final desired monomer 8 was also isolated in the coupling step, presumably due to hydrolysis of the allyl ester in the iron reduction step. The remaining allyl ester 7 was deallylated via Pd(PPh3)4 to afford the monomer 8 in 51% yield. Db2 Synthesis Db2 was prepared through a convergent
Assembly strategy for thieno[3,2-b]thiophenes via a disulfide intermediate derived from 3-nitrothiophene-2,5-dicarboxylate
Beilstein J. Org. Chem. 2025, 21, 2489–2497, doi:10.3762/bjoc.21.191
- reactions, probably involving ester hydrolysis or alkylating agent decomposition, can be avoided by omitting the external base. In addition, Na2S2O4 was investigated as a reductant in a DMF/water 9:1 (v/v) mixture at room temperature (Table 2, entry 6). In the presence of both K2CO3 and the alkylating agent
- acidification, however, the reaction afforded mixtures of the desired products and the corresponding carboxylic acids due to partial hydrolysis of the ester groups. This behavior was observed during cyclization of substrates 4a and 5a. In the case of substrate 6b, treatment with NaOMe resulted primarily in the
Palladium-catalyzed regioselective C1-selective nitration of carbazoles
Beilstein J. Org. Chem. 2025, 21, 2479–2488, doi:10.3762/bjoc.21.190
- NH-unsubstituted carbazole bearing a nitro group by removing the pyridyl directing group [58]. Treatment of compound 2a with methyl triflate, followed by hydrolysis with sodium hydroxide, successfully delivered the deprotected carbazole 3 in 53% yield (Scheme 4b). Next, we demonstrated the reduction
Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds
Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185
- with a yield of 53% yield. The excess of base (t-BuOK) caused simultaneous decarboxylation and hydrolysis of ester 37, forming the new nortriterpenoid 39 with a pentacyclic ring A (Scheme 7). In the work of Rath et al. [32], a similar method was proposed for the interconversion of cycles in the
Synthetic study toward vibralactone
Beilstein J. Org. Chem. 2025, 21, 2376–2382, doi:10.3762/bjoc.21.182
- ketal moiety was removed and the resulting intermediate underwent Wittig olefination to yield vinyl chloride 20. Subsequent hydrolysis and intramolecular esterification furnished intermediate 21, which was then subjected to C–H insertion [42][43][44]. To our disappointment, this ring closure still did
Comparative analysis of complanadine A total syntheses
Beilstein J. Org. Chem. 2025, 21, 2334–2344, doi:10.3762/bjoc.21.178
- , followed by acetylation of the resulting propargylic alcohol afforded 17 which was further advanced to 18 via copper-catalyzed selective displacement of the propargyl acetate with benzylamine and hydrolysis of the primary acetate. The primary alcohol of 18 was activated with PPh3/CCl4, triggering an
- regioselectivity and gave the desired cycloadduct 24 as the major product in 56% yield. From here on, removal of the TMS group with TBAF, followed by hydrogenolytic removal of the benzyl group and acidic hydrolysis of the formyl group, completed Siegel’s total synthesis of complanadine A. In addition, this
- underwent ketone release and amine-ketone condensation to form iminium ion 27. Under the same acidic conditions, enamide 26 underwent hydrolysis and tautomerization to form enol 28. Conjugate addition of enol 28 to iminium ion 27 gave 29 for the subsequent intramolecular Mannich cyclization to deliver 30
Recent advances in Norrish–Yang cyclization and dicarbonyl photoredox reactions for natural product synthesis
Beilstein J. Org. Chem. 2025, 21, 2315–2333, doi:10.3762/bjoc.21.177
- southern furan moiety of 69. Finally, hydrolysis of the carbonate followed by oxidation of the resulting diol completed the Norrish–Yang cyclization precursor gracilisoid A (49). Irradiation of 49 under anaerobic conditions with a CFL, followed by treatment with silica gel, successfully generated a pair of
Halogenated butyrolactones from the biomass-derived synthon levoglucosenone
Beilstein J. Org. Chem. 2025, 21, 2297–2301, doi:10.3762/bjoc.21.175
- sofosbuvir (2). Fluorination at C2 in the nucleoside results in metabolic stability and resistance to hydrolysis as it destabilizes the formation of a C1 oxocarbenium ion [5][6]. Trifluoromethylated γ-butyrolactones also find applications as antiviral agents, for example, lactone 4 which has activity against
- transfer all three chlorine atoms [32], dichlorinated ketone 10a was obtained in 88% yield following acidic workup. Similarly, treatment of enamine 9a with 3.0 equivalents of N-bromosuccinimide and acidic hydrolysis gave dibrominated material 10b in excellent yield. This procedure is attractive due to the
- the intermediate formate ester. Fluorination of enamine 9a with Selectfluor (SF) resulted only in hydrolysis with conditions adapted from Peng and Shreeves work [28]; and likewise, the base-promoted (KOt-Bu, LHMDS) fluorination of ketone 6 with Selectfluor was unsuccessful. However, when ketone 6 was
Enantioselective radical chemistry: a bright future ahead
Beilstein J. Org. Chem. 2025, 21, 2283–2296, doi:10.3762/bjoc.21.174
- and imidoyl chlorides) in the presence of CuBArF4/bisoxazoline L4 catalyst, an acid co-catalyst, and iridium photocatalyst form chiral oxazolines 29 in good yields and excellent enantioselectivities (82–97% ee) (Scheme 6). Chiral β-aminoalcohols 30 can be obtained by the hydrolysis of 29. Another
Pathway economy in cyclization of 1,n-enynes
Beilstein J. Org. Chem. 2025, 21, 2260–2282, doi:10.3762/bjoc.21.173
- cyclization, and hydrolysis, exclusively producing cis-tetrahydropyridin-4-one derivatives 77 (Scheme 16, path b). Mechanistic studies revealed that intermediate 74 could be stabilized by NHC ligands to facilitate 1,5-acyl migration, whereas phosphine ligands could accelerate proton dissociation in
- intermediate 76 to drive hydrolysis. This methodology tolerates structurally diverse 1,7-enyne esters and generates defined cis-1,2,3,6-tetrahydropyridine scaffolds, which serve as synthetic intermediates for complex natural products and pharmacologically relevant heterocyclic frameworks. In 2016, Jiang group
Electrochemical cyclization of alkynes to construct five-membered nitrogen-heterocyclic rings
Beilstein J. Org. Chem. 2025, 21, 2173–2201, doi:10.3762/bjoc.21.166
- anodic oxidation and AcO− capture. The hydrolysis of F then occurred to afford the final product 26a. This protocol featured with some advantages such as without any oxidants and metal catalysts, simple operation, good yields, high selectivity and wide substrate scope. Isoindolinone could be also
- vinyl radical intermediate D. The radical in D reacted with the pyridyl N atom regioselectively to form a tricyclic radical E, which proceeded one-electron oxidation/hydrolysis afforded 49. Additionally, the imidazopyridines could be constructed through electrochemical intramolecular [3 + 2] annulation
C2 to C6 biobased carbonyl platforms for fine chemistry
Beilstein J. Org. Chem. 2025, 21, 2103–2172, doi:10.3762/bjoc.21.165
- from lignocelluloses [163]. The hydrolysis and dehydration process of hemicellulose can be accomplished in water or in aqueous-based biphasic systems in the presence of mineral acids (such as H2SO4, HCl) and organic acids (such as HCOOH, CH3SO3H). The acid catalysts used for furfural production range
- hydrolysis (Scheme 59). Furfural was employed as starting scaffold in a protocol developed to form acetals as fuel additives. The acyclic acetal is generated in situ from crude furfural with propanol in dimethyl carbonate using a nanoporous aluminosilicate material Al-13-(3.18) as catalyst, and then
- , pharmaceuticals or high added value chemicals [215][216][217][218][219][220][221][222][223]. Its first commercial production began in the 1940s. Its preparation from biomass involves several different possible pathways. One is the C5 sugar route starting from xylose as an example, relying on acid hydrolysis of
The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products
Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164
- =C6 double bond to afford triacetate 60 as a single diastereoisomer. Base-promoted hydrolysis and concomitant oxidation under oxygen atmosphere gave vicinal diketone 61. Finally, the introduction of mono-bromo and di-bromo atoms achieved the total synthesis of (−)-hamigeran B (11) and (−)-4
- the A- and D-rings of 96, respectively, delivering the methyl enol ether 98. Finally, allylic oxidation [76], α-methylation and reduction of 98 followed by hydrolysis accomplished the first total synthsis of (−)-conidiogenone F (21). After achieving the aforementioned success, the authors continued to
- give (15R)-110 and (15S)-110 in 65% and 54% yield, respectively. Subsequently, ten functional group manipulations of the diastereomeric mixture 110 produced ketoester 111. Finally, the introduction of conjugated double bond in 111 followed by hydrolysis of the methyl ester to carboxylic acid and DCC
Discovery of cytotoxic indolo[1,2-c]quinazoline derivatives through scaffold-based design
Beilstein J. Org. Chem. 2025, 21, 2062–2071, doi:10.3762/bjoc.21.161
- interest, compound 2 applied as a useful substrate for a Baeyer–Villiger oxidation mediated by oxone, which selectively converted the aldehyde to the formate ester, yielding 6-oxo-5,6-dihydroindolo[1,2-c]quinazolin-12-yl formate (4). Subsequent hydrolysis of 4 furnished indolo[1,2-c]quinazoline-6,12-dione
Bioinspired total syntheses of natural products: a personal adventure
Beilstein J. Org. Chem. 2025, 21, 2048–2061, doi:10.3762/bjoc.21.160
- , Wittig reaction with MOMPPh3Cl and LDA gave the putative methyl enol ether, which could be directly converted into 1,3-dithiane 12 with propane-1,3-dithiol. Nucleophilic addition to chiral epoxide 13 and oxidative hydrolysis of 1,3-dithiane to ketone delivered chiral β-hydroxyketone 14. Evans−Tishchenko
- underwent dehydroxylation protocol involving base-promoted mesylate elimination and catalytic hydrogenation reactions, providing 31a. Reduction of lactam and ester in one pot with LiAlH4 and acid-promoted hydrolysis of ketal protection to ketone furnished 32a. Finally, oxidation of the primary alcohol to
- . This oxa-carbenium cation could also undergo hydrolysis to provide a linear skeleton with a hydroxy ketone moiety, and this hydrolysis process is reversible. It is worth noting that Zhou explored the chemical conversion of the eupodienone skeleton to the eupomatilone skeleton through acid-promoted
Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis
Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151
- norlignans hyperione A and ent-hyperione B was reported by the Deska group (Scheme 4) [33]. The synthesis commenced with a two-step conversion of ketone 22 to alkyne 23. Pd-catalyzed Tsuji-type reaction with zinc reagent 24, followed by acetonide hydrolysis, furnished allenic diol 25. Treating allenic diol
- 25 with vinyl butanoate and PPL delivered monoester 26 in 92% yield (99% ee). The axial chirality was transferred to the C7’ stereocenter through a Ag(I)-catalyzed cycloisomerization of the allenol, constructing the dihydrofuran ring. Lipase-catalyzed ester hydrolysis provided allylic alcohol 27
- sequence comprising TBS protection, ester hydrolysis, mesylation, and hydride reduction. In 2014, Tokuyama and co-workers accomplished the total synthesis of (−)-petrosin and (+)-petrosin, two marine-derived bisquinolizidine alkaloids [45]. They first completed the synthesis of (−)-petrosin (84) (Scheme
Systematic pore lipophilization to enhance the efficiency of an amine-based MOF catalyst in the solvent-free Knoevenagel reaction
Beilstein J. Org. Chem. 2025, 21, 1854–1863, doi:10.3762/bjoc.21.144
- environment, suppressing the hydrolysis reaction that would return the starting materials [36]. Thus, in this work, we investigate the influence of pore lipophilicity on the amine-catalyzed Knoevenagel condensation. The Knoevenagel condensation reaction is a vital organic reaction involving the condensation
Photoswitches beyond azobenzene: a beginner’s guide
Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143
[3 + 2] Cycloaddition of thioformylium methylide with various arylidene-azolones in the synthesis of 7-thia-3-azaspiro[4.4]nonan-4-ones
Beilstein J. Org. Chem. 2025, 21, 1791–1798, doi:10.3762/bjoc.21.141
- thermodynamically stable cis- and trans- isomers were also obtained in the reaction with azomethine ylides [20]. Finally, we performed preliminary derivatization studies of the obtained spiro-tetrahydrothiophenes. Compounds 7 and 9 demonstrated remarkable stability under both acidic and basic hydrolysis conditions
Research progress on calixarene/pillararene-based controlled drug release systems
Beilstein J. Org. Chem. 2025, 21, 1757–1785, doi:10.3762/bjoc.21.139
- supramolecular polymer with suberyl dicholine (DiCh) as the axle, with α-CD as the thread wheel and bisSC4A macrocycles as the iterative end cap units. Due to the hydrolysis of DiCh by cholinesterase, the formed supramolecular polymer assembly can be dispersed through enzymatic reactions. They successfully
Convenient alternative synthesis of the Malassezia-derived virulence factor malassezione and related compounds
Beilstein J. Org. Chem. 2025, 21, 1730–1736, doi:10.3762/bjoc.21.135
- DCC-induced condensation of phenylacetic acid reported by Bhandari and Ray [22] and others [23][24][25][26][27]. Initially, we converted indole-3-acetic acid to its methyl ester, followed by protection of the indole nitrogen with a Boc group and subsequent hydrolysis of the methyl ester to regenerate
Approaches to stereoselective 1,1'-glycosylation
Beilstein J. Org. Chem. 2025, 21, 1700–1718, doi:10.3762/bjoc.21.133
- traceless hydrolysis of β-GlcN-derived allyl glycosides with retention of the anomeric configuration [102]. Anomeric deallylation was achieved through an initial double-bond isomerization to the propenyl moiety, followed by oxidation of the glycosidic prop-1-enyl group to a formyl group, as in 111, with
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