Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• work simply by bringing substrates arbitrarily close to a potentially reactive group [99][100]. One rare but important exception is Breslow’s use of two tethered cyclodextrins to locate hydrophobic ester substrates next to a metal ion. Breslow’s catalyst accelerates the hydrolysis of esters and

Synthesis of imidazo[4,5-e][1,3]thiazino[2,3-c][1,2,4]triazines via a base-induced rearrangement of functionalized imidazo[4,5-e]thiazolo[2,3-c][1,2,4]triazines

• Dmitry B. Vinogradov,
• Alexei N. Izmest’ev,
• Angelina N. Kravchenko,
• Yuri A. Strelenko and
• Galina A. Gazieva

Beilstein J. Org. Chem. 2023, 19, 1047–1054, doi:10.3762/bjoc.19.80

• functionalized imidazo[4,5-e]thiazolo[3,2-b]-1,2,4-triazine derivatives into new heterocyclic systems. Alkaline hydrolysis of esters 1a,b. aDetermined by 1H NMR spectroscopy; bisolated yields. Synthesis of potassium imidazo[4,5-e][1,3]thiazino[2,3-c][1,2,4]triazine-7-carboxylates. Plausible rearrangement

Synthesis of trifluoromethyl ketones by nucleophilic trifluoromethylation of esters under a fluoroform/KHMDS/triglyme system

• Yamato Fujihira,
• Yumeng Liang,
• Makoto Ono,
• Kazuki Hirano,
• Takumi Kagawa and
• Norio Shibata

Beilstein J. Org. Chem. 2021, 17, 431–438, doi:10.3762/bjoc.17.39

• examined [46]. Trifluoromethyl ketones (TFMKs) are valuable fluorine-containing synthetic targets of bioactive compounds [55][56] that behave as mimics of the tetrahedral transition-state intermediate of enzymatic hydrolysis of esters and amides by stabilizing their hydrates (Figure 1a) [57]. In fact, the

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• enantioselective functional group interconversions on prochiral or racemic difluorocyclopropane and difluorocyclopropene derivatives have provided important ways of obtaining enantiomerically pure cyclopropanes. The key reactions in this context are the enzyme-catalyzed formation and hydrolysis of esters and the

On the hydrolysis of diethyl 2-(perfluorophenyl)malonate

• Ilya V. Taydakov and
• Mikhail A. Kiskin

Beilstein J. Org. Chem. 2020, 16, 1863–1868, doi:10.3762/bjoc.16.153

• . Keywords: decarboxylation; fluorinated aromatic compounds; hydrolysis of esters; 2-(perfluorophenyl)acetic acid; 2-(perfluorophenyl)malonic acid; Introduction 2-Phenylmalonic acid (1) and its esters are useful and versatile intermediates in the synthesis of many practically important compounds, e.g

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• derivatives by HF/Py The ring opening reaction of aziridines 138a,b by treatment with hydrogen fluoride in pyridine afforded 3-fluorophenylalanine esters 139a,b. The subsequent enzymatic hydrolysis of esters 139a,b gave the threo-isomer 136 in an enantiomerically pure form [68][69] (Scheme 31). On the other

An amine protecting group deprotectable under nearly neutral oxidative conditions

• Shahien Shahsavari,
• Chase McNamara,
• Mark Sylvester,
• Emily Bromley,
• Savannah Joslin,
• Bao-Yuan Lu and
• Shiyue Fang

Beilstein J. Org. Chem. 2018, 14, 1750–1757, doi:10.3762/bjoc.14.149

• , the dM-Dmoc group is expected to be more stable under nucleophilic conditions, which will allow many transformations including base hydrolysis of esters and amides, hydride reduction of carbonyl compounds, and a wide range of nucleophilic substitution reactions to be carried out without losing the

Regioselective decarboxylative addition of malonic acid and its mono(thio)esters to 4-trifluoromethylpyrimidin-2(1H)-ones

• Sergii V. Melnykov,
• Andrii S. Pataman,
• Yurii V. Dmytriv,
• Svitlana V. Shishkina,
• Mykhailo V. Vovk and
• Volodymyr A. Sukach

Beilstein J. Org. Chem. 2017, 13, 2617–2625, doi:10.3762/bjoc.13.259

• obtained by the cleavage of the N3-PMB substituent on short heating in TFA (see Table 4). It has been shown that acids 4a,f–m can be synthesized alternatively by alkaline hydrolysis of esters 6a,f–m (see Supporting Information File 1 for full experimental data). The ester group at position 5 remained

Hydrolysis, polarity, and conformational impact of C-terminal partially fluorinated ethyl esters in peptide models

• Vladimir Kubyshkin and
• Nediljko Budisa

Beilstein J. Org. Chem. 2017, 13, 2442–2457, doi:10.3762/bjoc.13.241

• of esters 1–5 at pH 11. Nonetheless, for the peptide esters 8b, 9b and 10b, the experimental decay (Figure 7) of the ester concentration resembled pseudo-zero order kinetics, which was also observed for another amino acid ester hydrolysis not shown here. Both fittings to the zero (Equations 6 and 7

• abundant in the unfolded protein states [91]. Hydrolytic stability in peptides Finally, we tested hydrolytic stability in esterified peptides 8b, 9b and 10b by observing hydrolysis of the ester using 19F NMR in buffered deuterium oxide (pH 7). We expected pseudo-first order kinetics as for the hydrolysis

Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane

• Mohammed Salah Ayoup,
• David B. Cordes,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2015, 11, 2671–2676, doi:10.3762/bjoc.11.287

• previously reported [8]. Palladium catalysed carboxylation [9] was explored with aryl iodides 5 or 6/7 as a mixture, and these gave the corresponding ethyl esters 8 and 9/10, respectively. The meta and para esters 9 and 10 were easily separated by chromatography. Hydrolysis of esters 8–10 using

Superoxide chemistry revisited: synthesis of tetrachloro-substituted methylenenortricyclenes

• Basavaraj M. Budanur and
• Faiz Ahmed Khan

Beilstein J. Org. Chem. 2014, 10, 2531–2538, doi:10.3762/bjoc.10.264

• ][11][12][13][14][15], hydrolysis and substitution reactions [16][17][18]. Filippo and co-workers [19][20][21][22] have extensively studied the substitution reactions of alkyl halides and tosylates; oxidative cleavage reactions and hydrolysis of esters. Frimer and co-workers [23][24] have studied its

Chemical modification allows phallotoxins and amatoxins to be used as tools in cell biology

• Jan Anderl,
• Hartmut Echner and
• Heinz Faulstich

Beilstein J. Org. Chem. 2012, 8, 2072–2084, doi:10.3762/bjoc.8.233

• 2b possess comparable affinities to actin (Table 1), but differ in their IC50 values by a factor of ca. 300. The effect is presumably a consequence of the faster hydrolysis of esters over amides by intracellular hydrolases. Polycationic derivatives of phalloidin, such as the polylysine conjugates