Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• exchange and dispersion interactions in CHCl3 in relation to DMSO are the driving forces behind the placement of sec-amine molecules into the R[4]A cavity and the formation of “in” type complexes. Keywords: complexes; DFT calculations; hydrogen bond; resorcin[4]arene; supramolecular chemistry

• transferred from the hydroxy group of R[4]A to the amine molecule, forming a hydrogen bond between the proton of the positively charged amino group and the oxygen anion in the R[4]A molecule (ArO−···H+NHR2). For sec-amine molecules such as morpholine and N-methylpiperazine, an “out” complex is formed by

• hydrogen bonding between the proton of the hydroxy group of R[4]A and the nitrogen atom of the amine molecule (ArOH···NHR2). In CHCl3, the amine molecule partially resides within the R[4]A cavity and the formed complex is stabilized by a hydrogen bond between the hydroxy group of R[4]A and the nitrogen

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• numerous similar attributes, halogen bonding has also proven to be a viable alternative in methodologies that rely on hydrogen bond initiation. For example, both halogen- and hydrogen bonding can be used in supramolecular chemistry as the binding mechanism in photoresponsive receptors [73][74][75][76][77

Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• in 83 and the enantioregulation was achieved by BINOL-derived chiral phosphoric acid P22. An amine functionality was crucial in the isoxazole ring to enhance the nucleophilicity of the adjacent carbon atom. In addition, the amine hydrogen forms an H-bond with the catalyst along with another hydrogen

• bond formed between the imine nitrogen of 49 and the catalyst’s OH group (see transition state 84). These dual H-bonding interactions were assisted by a π–π interaction between the arene rings of both the electrophile and nucleophile that helped in the formation of a stereodefined transition state. The

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• amines 52 with 2,5-DMTHF (2) under a L-(+)-tartaric acid-choline chloride based deep eutectic solvent as green medium (Scheme 25a). Deep eutectic solvents (DESs) are mainly synthesized by mixing quaternary ammonium salts and hydrogen-bond donors. In this study, various combinations of salts and hydrogen

• bond donating groups were investigated. Among these, the DES prepared by mixing quaternary ammonium salts choline chloride (ChCl) and the hydrogen-bond donor L-(+)-tartaric acid gives the best result. Moreover, L-(+)-tartaric acid–ChCl acts as both solvent and catalyst for pyrrole synthesis. This

Mechanochemical solid state synthesis of copper(I)/NHC complexes with K₃PO₄

• Ina Remy-Speckmann,
• Birte M. Zimmermann,
• Mahadeb Gorai,
• Martin Lerch and
• Johannes F. Teichert

Beilstein J. Org. Chem. 2023, 19, 440–447, doi:10.3762/bjoc.19.34

• inactive complexes (see Supporting Information File 1 for details). This also supports the notion that during catalytic ester hydrogenation, the guanidinium moiety acts as a hydrogen bond donor to the esters [48]. The formation of a CO2 adduct hinders the ability to form hydrogen bonds. Furthermore

Dipeptide analogues of fluorinated aminophosphonic acid sodium salts as moderate competitive inhibitors of cathepsin C

• Karolina Wątroba,
• Małgorzata Pawełczak and
• Marcin Kaźmierczak

Beilstein J. Org. Chem. 2023, 19, 434–439, doi:10.3762/bjoc.19.33

• as potential inhibitors of cathepsins. The phosphorus atom by default should mimic the tetrahedral intermediate, but this role may also be played by the hydroxy group present in hydroxyphosphonates, which mimic the carbonyl carbon in the peptide bond by forming a hydrogen bond with the amino group of

Asymmetric synthesis of a stereopentade fragment toward latrunculins

• Benjamin Joyeux,
• Antoine Gamet,
• Nicolas Casaretto and
• Bastien Nay

Beilstein J. Org. Chem. 2023, 19, 428–433, doi:10.3762/bjoc.19.32

• -induction of the aldol stereocenter by β-alkoxy ketone 9, leading to an (S)-configuration [18][19][20]. This control is supposed to follow a boat transition state A stabilized by a formyl hydrogen bond [30]. It is known to be dependent on the nature of the β-alkoxy substituent, being particularly favoured

Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles

• Bilge Banu Yagci,
• Selin Ezgi Donmez,
• Onur Şahin and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2023, 19, 66–77, doi:10.3762/bjoc.19.6

• -unsaturated acyl chlorides to afford substituted α-methylene-γ-lactam heterocycles. The reactions proceed effectively in the presence of catalytic (20 mol %) amounts of AgOTf as an anion exchange agent or hydrogen-bond donors such as squaramides and thioureas as anion-binding organocatalysts. The aza-Nazarov

• isolated in 54% yield (Table 1, entry 8). The exchange of chloride with the non-coordinating BF4− anion, driven by the precipitation of NaCl, is proposed to be responsible for this positive result. Next, we turned our attention to the use of hydrogen-bond donors as anion-binding catalysts [57][58]. To this

• ). Finally, we investigated the activity of the achiral thiophosphoric triamide 13 as a triple hydrogen-bond donor [67]. With the use of 1.2 equiv of 13 at 23 °C, product 7b was isolated in 25% yield (Table 1, entry 16). Overall, while AgOTf still appeared to be the best reagent to be used in catalytic

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• protected tryptamine starting materials. The utilization of a chiral phosphate base is essential for the formation of a hydrogen bond between phosphate and tryptamines, allowing the decrease of the oxidation potential. This concept was used for the synthesis of pyrroloindoline natural products (Scheme 17

Total synthesis of grayanane natural products

• Nicolas Fay,
• Rémi Blieck,
• Cyrille Kouklovsky and
• Aurélien de la Torre

Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181

• optimization showed that chiral squaramide 47 developed by Jacobsen’s group significantly accelerated the Mukaiyama reaction compared to TMSOTf or TiCl4 thanks to chiral hydrogen bond-donor effect [35]. After Sakurai cyclization promoted by EtAlCl2, the desired product 48 was obtained with the required

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• coupling, or deprotonation followed by the functionalization of α- and β-positions of the starting aldehyde. NHC-catalyzed photochemical processes [64] and oxidative cyclizations with heterocycle formation [65] were reviewed previously. Acidic molecules or hydrogen-bond donors are used as organocatalysts

• oxaziridinium organocatalysis was developed recently [138]. The advantage of this method is the compatibility with secondary alcohol groups, which are not oxidized and can be used as a directing moiety. The use of HFIP as a strong hydrogen bond donor solvent protecting alcohols from oxidation was considered as

Preparation of β-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene

• Konstantin Lebedinskiy,
• Volodymyr Lobaz and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2022, 18, 1596–1606, doi:10.3762/bjoc.18.170

• 13 (β-CD) has also shown poor solubilizing activity. We suggest that the presence of hydroxy groups on the secondary rim of CD allows the hydrogen bond formation between two molecules, creating a capsule (tail-to-tail interaction, Figure 6a). It seems the generation of such capsules in solution

Experimental and theoretical studies on the synthesis of 1,4,5-trisubstituted pyrrolidine-2,3-diones

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Nguyen Ngoc Tri,
• Luc Van Meervelt,
• Nguyen Tien Trung and
• Wim Dehaen

Beilstein J. Org. Chem. 2022, 18, 1140–1153, doi:10.3762/bjoc.18.118

• -Trisubstituted pyrrolidine-2,3-dione derivatives were prepared from the above mentioned 2-pyrrolidinone derivatives and aliphatic amines, which exist in enamine form and are stabilized by an intramolecular hydrogen bond. A possible reaction mechanism between 3-pyrroline-2-one and aliphatic amine (CH3NH2) was

• 4a–c in DMSO [46], a hydrogen-bond accepting solvent (Scheme 3). To clarify further this statement, DFT calculations were performed at the B3LYP/6-311++G(2d,2p)//B3LYP/6-31+G(d,p) level of theory as given in Table 2 and Table 3. The theoretical results show that structure 4a is more stable than 4a

• ···O intramolecular hydrogen bond (distance ca. 1.7–1.8 Å) (cf. Figures 4–6). The isomerization of 4a/4a’ is extremely fast due to the high rate constant of about 1012 s−1 at 298 K, calculated by the transitional state theory method and quantum tunneling effect [47]. It is thus impossible to

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• , is consistent with intramolecular hydrogen bond interaction, which is accompanied by a reduction of the exchange rate of the NH proton. In DMSO, we observe reduced NH linewidths, consistent with the fact that this solvent has strong hydrogen bonding and solvation abilities which reduce significantly

• Information File 1). The lowest energy was found for χ1 = 124°, an angle value slightly higher than those found in the crystallographic structure of compound 2 (111 and 116° for conformation B, Table 2). This difference may be a result of the 6-membered intramolecular hydrogen bond formed in the monomer model

• geometry by the N-methylamino side chain, the presence of a hydrogen bond NH donor group is a key element in controlling the main-chain conformation and side chains orientation. It should be noted that to date, the presence of D–H donor groups on the side chains has been little exploited to control the

An isoxazole strategy for the synthesis of 4-oxo-1,4-dihydropyridine-3-carboxylates

• Timur O. Zanakhov,
• Ekaterina E. Galenko,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2022, 18, 738–745, doi:10.3762/bjoc.18.74

• due to their specific characteristics such as basicity, hydrogen bond forming ability, water solubility, and especially because of pyridine rings are bioisosteres of amines, amides, N-heterocyclic rings and benzene rings [1][2][3][4][5]. A special type of pyridine, the 4-pyridones, is also fairly well

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• the binary and ternary complex structures indicated that the Tyr224 residue rotates by 115° toward the opposite side of the iron center and forms a hydrogen bond with T134. The resulting distance between the Tyr224 hydroxy group and the iron center is 8.5 Å. These observations support the CarC-like

• the substrate. The substrate asnovolin A binds in the closed conformation through a hydrogen bond network with active site residues (Figure 4D). In this binding mode, C7' of the substrate is 4.2 Å away from the iron center, which is shorter than the distance between the iron center and C13 (6.5 Å

• -containing natural products. Structures of COXs [52][53]. (A) The overall structure of ovine COX-1. (B and C) Comparison of the cyclooxygenase sites of (B) COX-1 and (C) COX-2 in complex with AA. Yellow dashed lines show hydrogen bond interactions. The blue dashed line shows the distance between Tyr385 and

Mechanochemical halogenation of unsymmetrically substituted azobenzenes

• Dajana Barišić,
• Mario Pajić,
• Ivan Halasz,
• Darko Babić and
• Manda Ćurić

Beilstein J. Org. Chem. 2022, 18, 680–687, doi:10.3762/bjoc.18.69

• four mechanistic pathways could be involved in this reaction [51]. Three of them involve oxidative addition followed by reductive elimination. Neutral NBS or the hydrogen bond complex NBS∙∙∙TsOH are bromine donors in two of them, while protonated NBS is engaged in the third. The fourth mechanism

• proceeds by electrophilic cleavage with neutral NBS or the hydrogen bond complex NBS∙∙∙TsOH as a bromine source. Here we present the mechanochemical selective halogenation of unsymmetrically substituted azobenzenes by NXS (X = Cl, Br, or I). The liquid-assisted grinding of para-halogenated derivatives of

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• of the guest molecule was proven by UV–vis and IR spectroscopy. The multicomponent prism (Figure 3) was finally utilized as a heterogeneous catalyst for Michael and Diels–Alder (DA) reactions in water, representing an uncommon hydrogen-bond donating heterogeneous catalyst [59]. Intrigued by the

A study of the photochemical behavior of terarylenes containing allomaltol and pyrazole fragments

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2022, 18, 588–596, doi:10.3762/bjoc.18.61

• considered photoprocess. Probably, the DMF molecule forms an intermolecular hydrogen bond with the hydroxy group of the allomaltol fragment leading to complete suppression of the ESIPT process. Finally, AcOH was used as a solvent for the photochemical synthesis of α-hydroxy-1,2-diketone 14a. The starting

New advances in asymmetric organocatalysis

• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 240–242, doi:10.3762/bjoc.18.28

• transformations using chiral Brønsted acids, Brønsted base, and hydrogen bond donors. Recently noncovalent activation continues to expand into other types of weak attractive interactions such as halogen and chalcogen bonds. Not surprisingly, all activation modes allow further expansion and diversification via a

Asymmetric organocatalytic Michael addition of cyclopentane-1,2-dione to alkylidene oxindole

• Estelle Silm,
• Ivar Järving and
• Tõnis Kanger

Beilstein J. Org. Chem. 2022, 18, 167–173, doi:10.3762/bjoc.18.18

• bifunctional hydrogen-bonding catalyst would activate both CPD via a tertiary amino group of a quinuclidine moiety acting as a base via anion-binding, and an oxindole through the squaramide or thiourea moieties of the catalyst as hydrogen bond donors (Figure 1) [29][30][31][32]. Therefore, squaramide and

Efficient and regioselective synthesis of dihydroxy-substituted 2-aminocyclooctane-1-carboxylic acid and its bicyclic derivatives

• İlknur Polat,
• Selçuk Eşsiz,
• Uğur Bozkaya and
• Emine Salamci

Beilstein J. Org. Chem. 2022, 18, 77–85, doi:10.3762/bjoc.18.7

• seen that the conformation is quite appropriate for the formation of lactone 10. The hydrogen bond between the C=O group of methoxy ester and NH group of the carbamate in 7 provides an appropriate conformation for the formation of lactone 10. Additionally, according to the conformational analysis of

Efficient synthesis of ethyl 2-(oxazolin-2-yl)alkanoates via ethoxycarbonylketene-induced electrophilic ring expansion of aziridines

• Yelong Lei and
• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 70–76, doi:10.3762/bjoc.18.6

• hydrogen bond. Thus, the tautomerization favors to the left direction, forming D-form products, when α-diazo-β-diketones are as starting materials (R1 = alkyl and aryl), while it predominates to the right direction, generating 2-(alkoxycarbonyl)methyloxazolines as products, when alkyl α-diazo-β

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• space of the macrocycle. Cis and trans isomers share a fairly similar main conformation (c1, blue in the figure) with high population (31.8 and 27.9%, respectively). This conformation is stabilised by a hydrogen bond between the CO group of Ile and the NH group of Lys, and triggers the formation of a

Host–guest interaction and properties of cucurbit[8]uril with chloramphenicol

• Lin Zhang,
• Jun Zheng,
• Guangyan Luo,
• Xiaoyue Li,
• Yunqian Zhang,
• Zhu Tao and
• Qianjun Zhang

Beilstein J. Org. Chem. 2021, 17, 2832–2839, doi:10.3762/bjoc.17.194

• formation of a O–H···O hydrogen bond, in which the bond distance between O20 and O5 was 2.921 Å. It can be seen that the CPE molecule is distorted at the C51 atom and the bond angle between C53–C51–N34 was 103.30°, which makes the CPE molecule fixed and enter the cavity of Q[8]. Figure 2C shows the crystal