Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

• Oleg A. Levitskiy,
• Olga I. Aglamazova,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2022, 18, 1166–1176, doi:10.3762/bjoc.18.121

• ][26]. Donor–acceptor cyclopropanes constitute an easily available equivalent of all-carbon 1,3-zwitter-ions used in targeted synthesis of various alicyclic as well as carbo- or heterocyclic compounds [27][28][29][30]. The reactive synergy of the three-membered ring and the C–C bond polarization due to

Advances in mercury(II)-salt-mediated cyclization reactions of unsaturated bonds

• Sumana Mandal,
• Raju D. Chaudhari and
• Goutam Biswas

Beilstein J. Org. Chem. 2021, 17, 2348–2376, doi:10.3762/bjoc.17.153

• -containing mixture of diastereomeric alicyclic derivatives 59. The tetrahydropyrimidin-4(1H)-one-mercuri trifluoroacetate derivative 59 on successive treatment with NaBr and LiBH4 gives a mixture of tetrahydropyrimidin-4(1H)-one derivatives 60 in the diastereomeric ratio of 63:37 after separation by column

Regioselective N-alkylation of the 1H-indazole scaffold; ring substituent and N-alkylating reagent effects on regioisomeric distribution

• Ryan M. Alam and
• John J. Keating

Beilstein J. Org. Chem. 2021, 17, 1939–1951, doi:10.3762/bjoc.17.127

• , entry 22), its tosylate counterpart gave the corresponding N-1 regioisomer 10 with a high degree of N-1 regioselectivity (ratio N-1 (10):N-2 (11) = 76:1) under conditions A (Table 6, entry 1). Furthermore, conditions A could be successfully applied to the synthesis of benzyl and alicyclic indazole

• conversion (13%, combined N-1 and N-2 (see Supporting Information)) (Table 5, entry 5). However, employing the corresponding tosylate under identical conditions (NaH in THF (conditions A)) permitted improved conversion to the desired N-1 substituted alicyclic indazole 73 (78%, combined N-1 and N-2 (see

A new method for the synthesis of diamantane by hydroisomerization of binor-S on treatment with sulfuric acid

• Rishat I. Aminov and
• Ravil I. Khusnutdinov

Beilstein J. Org. Chem. 2020, 16, 2534–2539, doi:10.3762/bjoc.16.205

• compounds, an important place is occupied by diamond-like compounds called diamondoids, whose lower representatives belong to the homologous series C4n+6H4n+12. Owing to the rigid structure, diamondoids typically have high thermal stability and high reactivity compared with aliphatic and alicyclic saturated

A review of the total syntheses of triptolide

• Xiang Zhang,
• Zaozao Xiao and
• Hongtao Xu

Beilstein J. Org. Chem. 2019, 15, 1984–1995, doi:10.3762/bjoc.15.194

• butenolide 70. The second one is the reaction of alicyclic alcohol 73 with dimethylformamide dimethylacetal to give an allylic amide by means of a [2,3]-sigmatropic rearrangement of a carbene intermediate. Epoxidation the allylic amide with m-CPBA gave 74, followed by lithium hexamethyldisilazide-induced β

One-pot activation–alkynylation–cyclization synthesis of 1,5-diacyl-5-hydroxypyrazolines in a consecutive three-component fashion

• Christina Görgen,
• Katharina Boden,
• Guido J. Reiss,
• Walter Frank and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2019, 15, 1360–1370, doi:10.3762/bjoc.15.136

• substrate 4 all different types of (hetero)aromatic, aliphatic, and alicyclic substituents R3 are well tolerated in the sequence (Table 3, entries 1–10). The alkynes 2 can bear electron-donating and electron-withdrawing substituents R2 (Table 3, entries 1, 11–14), however, for the electron-poor cyano

Thiol-free chemoenzymatic synthesis of β-ketosulfides

• Adrián A. Heredia,
• Martín G. López-Vidal,
• Marcela Kurina-Sanz,
• Fabricio R. Bisogno and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2019, 15, 378–387, doi:10.3762/bjoc.15.34

• must be considered the additional bulky o-iodobenzyl substituent attached to the sulfur. The bulky alicyclic adamantyl α-substituent (compound 1r), was not accepted as substrate (Table 2, entry 18). The same results were obtained when an ester moiety was pending at α-position (1s, Table 2, entry 19

Copolymerization of epoxides with cyclic anhydrides catalyzed by dinuclear cobalt complexes

• Yo Hiranoi and
• Koji Nakano

Beilstein J. Org. Chem. 2018, 14, 2779–2788, doi:10.3762/bjoc.14.255

•  2, entry 2). The copolymerization with cyclohexene oxide (CHO), a common alicyclic epoxide in epoxide/CA copolymerization, also gave the corresponding alternating copolymer (Table 2, entries 3 and 4). The TOF of 244 h−1 was achieved at 60 °C, which was the highest one ever reported for a CHO/PA

Ring-opening metathesis of some strained bicyclic systems; stereocontrolled access to diolefinated saturated heterocycles with multiple stereogenic centers

• Zsanett Benke,
• Melinda Nonn,
• Márton Kardos,
• Santos Fustero and
• Loránd Kiss

Beilstein J. Org. Chem. 2018, 14, 2698–2707, doi:10.3762/bjoc.14.247

• transformations, cyclic dienes with different ring sizes might be considered to be important starting materials for the generation of structurally diverse molecules. Among the large number of possible transformations, the ring olefinic bond of alicyclic dienes may lead to valuable β-lactams [21][22][23] or γ

Learning from B₁₂ enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

• Keishiro Tahara,
• Ling Pan,
• Toshikazu Ono and
• Yoshio Hisaeda

Beilstein J. Org. Chem. 2018, 14, 2553–2567, doi:10.3762/bjoc.14.232

• confirmed by the spin-trapping technique followed by the ESR measurements. The B12-TiO2 hybrid catalyst also mediated the ring-expansion reactions of alicyclic ketones with carboxylic ester and bromomethyl groups (Scheme 11) [96][98]. The products involving six-, seven-, and eight-membered rings were

Fluorination of some highly functionalized cycloalkanes: chemoselectivity and substrate dependence

• Attila Márió Remete,
• Melinda Nonn,
• Santos Fustero,
• Matti Haukka,
• Ferenc Fülöp and
• Loránd Kiss

Beilstein J. Org. Chem. 2017, 13, 2364–2371, doi:10.3762/bjoc.13.233

• -amino ester stereo- and regioisomers, derived from unsaturated cyclic β-amino acids is described. The nucleophilic fluorinations involving hydroxy–fluorine exchange of some highly functionalized alicyclic diol derivatives have been carried out in view of selective fluorination, investigating substrate

• . Results and Discussion Our aim in this study was to explore the chemical behavior of some alicyclic, highly functionalized vicinal diol derivatives (accordingly possessing two fluorine precursor moieties in their structures) under fluorination protocols. During the past two decades multifunctionalized

• , cispentacin) are relevant antifungal agents [19]. Therefore we have selected some five and six-membered alicyclic dihydroxylated β-amino ester stereo- and regioisomers as model compounds [23][24][25][26], derived from cyclopentene or cyclohexene β-amino acids. These were used in order to evaluate their

Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

• Mathew J. Jones,
• Ricardo Callejo,
• Alexandra M. Z. Slawin,
• Michael Bühl and
• David O'Hagan

Beilstein J. Org. Chem. 2016, 12, 2823–2827, doi:10.3762/bjoc.12.281

• offer new possibilities for the design of performance molecules extending from organic materials research to medicinal chemistry. Selected fluorinated polar alicyclic scaffolds. X-ray structure of compound 4c. The image shows two molecules stacked with the non-fluorine face pointing to an adjacent

Terminal lipophilization of a unique DNA dodecamer by various nucleolipid headgroups: Their incorporation into artificial lipid bilayers and hydrodynamic properties

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2015, 11, 913–929, doi:10.3762/bjoc.11.103

• -, sesqui-, and diterpenes as well as single and double-chained alkyl groups (completed by an alicyclic alkyl group), have been introduced for the lipophilization of the pyrimidine nucleosides. The resulting nucleolipids were converted into their corresponding 2-cyanoethyl phosphoramidites 4b–9b. Figure 3

• 5-fluorouridine carrying an alicyclic O-2’,3’-cyclopentadecanylidene ring. As can be seen, the binding within or (more likely) at the lipid bilayer occurs relatively slowly within 55–60 min until the maximum brightness of the bilayer is reached. A single perfusion reduces the brightness to 55

Stereoselective synthesis of perillaldehyde-based chiral β-amino acid derivatives through conjugate addition of lithium amides

• Zsolt Szakonyi,
• Reijo Sillanpää and
• Ferenc Fülöp

Beilstein J. Org. Chem. 2014, 10, 2738–2742, doi:10.3762/bjoc.10.289

• proved to be versatile building blocks both in pharmacological developments and asymmetric syntheses [1][2][3][4][5][6][7][8]. Alicyclic and bicyclic chiral β-amino acids have played a key role in the synthesis of β-peptide-type foldamers, where through the selection of an appropriate alicyclic or

• secondary structure of foldamers, the introduction of well-designed hydrophilic or hydrophobic substituents on the alicyclic ring of β-amino acids can modify the fine structure of β-peptides. There are several powerful synthetic methods through which alicyclic or bicyclic β-amino acid enantiomers can be

• achiral anhydrides followed by Curtius degradation [18][19][20]. The highly stereoselective Michael addition of lithium amide-type nucleophiles to α,β-unsaturated esters also proved to be a very efficient and useful method for the preparation of alicyclic β-amino acids in homochiral form [21][22

Five-membered ring annelation in [2.2]paracyclophanes by aldol condensation

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2014, 10, 2021–2026, doi:10.3762/bjoc.10.210

• derivatives with annelated alicyclic rings. The formation of the tetraketone 9 by a Diels–Alder addition. The possible structures of the aldols formed from 9. The mechanism of the aldol cyclization. Dehydration of the aldol 12. Dehydration of the aldol 15. Hydrogen bonds [Å and °] for 12.CDCl3.a

Silica: An efficient catalyst for one-pot regioselective synthesis of dithioethers

• Samir Kundu,
• Babli Roy and
• Basudeb Basu

Beilstein J. Org. Chem. 2014, 10, 26–33, doi:10.3762/bjoc.10.5

• observed in the reaction of aliphatic thiols (acyclic or alicyclic), viz. n-pentane-1-thiol and cyclohexanethiol, with allyl bromide to afford the corresponding 1,3-dithioethers in 71% and 67% yield, respectively (Table 2, entries 14 and 16). In these cases, we did not detect any Markovnikov addition

Gold-catalyzed glycosidation for the synthesis of trisaccharides by applying the armed–disarmed strategy

• Abhijeet K. Kayastha and
• Srinivas Hotha

Beilstein J. Org. Chem. 2013, 9, 2147–2155, doi:10.3762/bjoc.9.252

• (15b,e) were not tolerated. The gem-dimethyl alkyne 15g showed a substantial improvement of the performance at 25 °C compared to the other alkynyl donors 15a–f (Table 1). However, the gem-dimethyl donor 15g was not preferred due to the shorter shelf life. The alicyclic derivatives 15h–j gave comparable

Efficient continuous-flow synthesis of novel 1,2,3-triazole-substituted β-aminocyclohexanecarboxylic acid derivatives with gram-scale production

• Sándor B. Ötvös,
• Ádám Georgiádes,
• István M. Mándity,
• Lóránd Kiss and
• Ferenc Fülöp

Beilstein J. Org. Chem. 2013, 9, 1508–1516, doi:10.3762/bjoc.9.172

• relatively short reaction time [18][19][20]. Recently, Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) has become the basis of the so-called click chemistry concept due to its wide applicability and efficiency. Over the past twenty years, alicyclic β-amino acids have attracted great interest among

• bioactive agents with anticancer, antibacterial, antiviral or analgesic effects (Figure 2) [25][26]. The alicyclic β-amino acids are key intermediates for the synthesis of a series of pharmaceutically relevant products [27], such as amino esters, amino alcohols, azides and heterocycles. Moreover, they are

• elapsed between the first contact of the ink with the bed and the moment when the blue colour appeared at the column outlet was measured. Examples of 1,2,3-triazoles with various biological activities. Selected bioactive alicyclic β-amino acids. Experimental setup for the CF reactions. 1,3-Dipolar azide

Space filling of β-cyclodextrin and β-cyclodextrin derivatives by volatile hydrophobic guests

• Sophie Fourmentin,
• Anca Ciobanu,
• David Landy and
• Gerhard Wenz

Beilstein J. Org. Chem. 2013, 9, 1185–1191, doi:10.3762/bjoc.9.133

• pressure; Introduction β-Cyclodextrin (β-CD, 1), the cyclic α(1→4) heptamer of glucose, is known to form inclusion compounds with a great variety of guests [1], such as derivatives of benzene [2][3], cyclohexane [4], adamantane [5][6], other alicyclic guests [7], and also inorganic molecules or ions [1][8

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• steps (high step economy). Keywords: alicyclic; bisallenes; cyclic; cycloadditions; cycloisomerization; isomerization; molecular complexity; step economy; Table of Contents Introduction Review Acyclic conjugated bisallenes 1.1 Synthesis of hydrocarbons 1.2 Synthesis of functionalized systems 1.3

The preferred conformation of erythro- and threo-1,2-difluorocyclododecanes

• Yi Wang,
• Peer Kirsch,
• Tomas Lebl,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2012, 8, 1271–1278, doi:10.3762/bjoc.8.143

• –F bond endo into the ring, and appear to benefit from C–CHF–C angle widening, which relaxes 1,4-H,H transannular interactions. Keywords: alicyclic chemistry; conformational analysis; cyclododecane; 19F NMR; organo-fluorine chemistry; transannular interactions; Introduction The conformation of

Synthesis, reactivity and biological activity of 5-alkoxymethyluracil analogues

• Lucie Brulikova and
• Jan Hlavac

Beilstein J. Org. Chem. 2011, 7, 678–698, doi:10.3762/bjoc.7.80

• )pyrimidines 68 and 69. The latter readily underwent nucleophilic attack by alkoxide ions to yield alicyclic or cyclic acetals 70–73 and 74, respectively, depending on the alcohol used. Uridine and arabinofuranosyl analogues: 5-Substituted uracil nucleosides where the sugar component is ribose or arabinose

Reciprocal polyhedra and the Euler relationship: cage hydrocarbons, C_nH_n and closo-boranes [B_xH_x]²⁻

• Michael J. McGlinchey and
• Henning Hopf

Beilstein J. Org. Chem. 2011, 7, 222–233, doi:10.3762/bjoc.7.30

• and will remain at the forefront of alicyclic chemistry until a stepwise synthesis of C60 is achieved. However, we note en passant that Scott, de Meijere and their colleagues have devised a rational route to C60 from a chlorinated precursor, C60H27Cl3, in which only the final ring closures were

Expanding the gelation properties of valine-based 3,5-diaminobenzoate organogelators with N-alkylurea functionalities

• Hak-Fun Chow and
• Chin-Ho Cheng

Beilstein J. Org. Chem. 2010, 6, 1015–1021, doi:10.3762/bjoc.6.114

• properties were extended from only aromatic solvents, to a wide range of other types of solvents such as alicyclic hydrocarbons, alcohols and polar solvents such as DMSO and DMF. It was also found that a longer N-alkylurea chain conferred improved gelation power and higher thermal stability as compared to

• alicyclic hydrocarbon, alcohols and even polar aprotic solvents such as DMSO and DMF by replacing the Cbz group with an N-alkylurea functionality (e.g., 2). In addition, the length of the alkyl chain –(CH2)nMe also exhibited some interesting effects on their gelation ability [15]. Results and Discussion

• alcoholic solvents and translucent gels in alicyclic hydrocarbon solvents, respectively. Hence, the range of the solvents that these new compounds can gel was significantly expanded by replacing the Cbz group with an N-alkylurea functionality. Based on these experiments, organogelators 2 with longer