Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

• section will commence by examining linear alkanes, then it will move on to examine cycloalkanes. In the case of linear alkanes, we will first consider what happens if fluorine is introduced at the end of the chain. The installation of fluorine converts the alkyl chain from a non-polar into a polar motif

• via multiple fluorines is seen with the trifluorinated cyclohexene 34: this molecule prefers the half-chair conformation in which σC–H → σ*C–F hyperconjugation with the flanking methylene groups is maximised (Figure 5) [50]. When discussing small-ring cycloalkanes, it is impossible to ignore a

• very high molecular dipoles. However, since the fluorination patterns in these cases do not really control or alter the ring pucker, they are outside the scope of this review. Finally, we will examine larger-ring cycloalkanes. Large rings have more degrees of freedom than small rings, and hence they

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• ). The reaction proceeded via the dehydrogenation of the alcohol, aldol condensation, and hydrogenation of α,β-unsaturated ketones. In 2019, Leitner and his group introduced an outstanding cascade BH approach for the synthesis of various substituted cycloalkanes by coupling diols and secondary alcohols

• intramolecular BH reaction for the formation of cycloalkanes from ketones and 1,n-diols [66]. Different substituted 1,5-diols were coupled with 1-(2,3,4,5,6-pentamethylphenyl)ethan-1-one using 4 mol % of catalyst Mn13 and 2 equiv of t-BuOK as base in t-AmOH at 140 °C for 36 h to give 51–98% yield of the six

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• have broad applications in synthesis. In 2019, Cai et al. developed a regioselective ligand-promoted CDC reaction between unactivated C(sp3)–H/C(sp3)–H bonds (Scheme 18) [79]. Different types of C(sp3)–H bond substrates, including cycloalkanes, cyclic ethers, and toluene derivatives without any

• -dicarbonyl compounds. Rare earth-metal-catalyzed CDC reaction. Visible-light-driven CDC of cycloalkanes with benzazoles. Photoinduced alkylation of quinoline with cyclic ethers. Photocatalyzed CDC reactions between α-C(sp3)–H bonds of ethers and C(sp2)–H bonds of aromatics.

Radical cation Diels–Alder reactions of arylidene cycloalkanes

• Kaii Nakayama,
• Hidehiro Kamiya and
• Yohei Okada

Beilstein J. Org. Chem. 2022, 18, 1100–1106, doi:10.3762/bjoc.18.112

• 183-8509, Japan 10.3762/bjoc.18.112 Abstract TiO2 photoelectrochemical and electrochemical radical cation Diels–Alder reactions of arylidene cycloalkanes are described, leading to the construction of spiro ring systems. Although the mechanism remains an open question, arylidene cyclobutanes are found

• to be much more effective in the reaction than other cycloalkanes. Since the reaction is completed with a substoichiometric amount of electricity, a radical cation chain pathway is likely to be involved. Keywords: arylidene cycloalkane; Diels–Alder reaction; radical cation; single-electron transfer

• unexpected finding that various spiro ring systems can be constructed by a radical cation Diels–Alder reaction of arylidene cycloalkanes. Results and Discussion The present work began with the reaction of β-methylanethole (1) with 2,3-dimethyl-1,3-butadiene (2) under TiO2 photoelectrochemical and

Copper-catalyzed multicomponent reactions for the efficient synthesis of diverse spirotetrahydrocarbazoles

• Shao-Cong Zhan,
• Ren-Jie Fang,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 796–808, doi:10.3762/bjoc.18.80

• [carbazole-2,3'-indolines], spiro[carbazole-3,5'-pyrimidines] and spiro[carbazole-3,1'-cycloalkanes] in satisfactory yields and with high diastereoselectivity. Keywords: Diels–Alder reaction; indole; indolo-2,3-quinodimethane; Levy reaction; tetrahydrocarbazole; spirooxindole; Introduction

• sustainable, general and practical, which providing facile access to important polysubstituted spiro[carbazole-3,3'-indolines], spiro[carbazole-2,3'-indolines], spiro[carbazole-3,5'-pyrimidines] and spiro[carbazole-3,1'-cycloalkanes] with good yields and high diastereoselectivity. This reaction actually

(Phenylamino)pyrimidine-1,2,3-triazole derivatives as analogs of imatinib: searching for novel compounds against chronic myeloid leukemia

• Luiz Claudio Ferreira Pimentel,
• Lucas Villas Boas Hoelz,
• Henayle Fernandes Canzian,
• Frederico Silva Castelo Branco,
• Andressa Paula de Oliveira,
• Vinicius Rangel Campos,
• Floriano Paes Silva Júnior,
• Rafael Ferreira Dantas,
• Jackson Antônio Lamounier Camargos Resende,
• Anna Claudia Cunha,
• Nubia Boechat and
• Mônica Macedo Bastos

Beilstein J. Org. Chem. 2021, 17, 2260–2269, doi:10.3762/bjoc.17.144

• phenylpiperazine group present in compound 3, we have simplified the side chain attached to the 1,2,3-triazole nucleus by including different groups, such as ester (2i,j), cycloalkanes (2e,f), a saturated heterocycle in 2g and an aromatic ring in 2h whose stereoelectronic and physicochemical characteristics vary

Volatile emission and biosynthesis in endophytic fungi colonizing black poplar leaves

• Christin Walther,
• Pamela Baumann,
• Katrin Luck,
• Beate Rothe,
• Peter H. W. Biedermann,
• Jonathan Gershenzon,
• Tobias G. Köllner and
• Sybille B. Unsicker

Beilstein J. Org. Chem. 2021, 17, 1698–1711, doi:10.3762/bjoc.17.118

• ]. Endophytic fungi themselves can produce VOCs. Currently, around 300 fungal VOCs have been characterized, including aliphatic alcohols, ketones, aldehydes, acids and esters, terpenoids, benzenoids, naphthalene derivatives, and cycloalkanes [25][26][27]. Endophytic fungal VOCs are frequently described to

Manganese/bipyridine-catalyzed non-directed C(sp³)–H bromination using NBS and TMSN₃

• Kumar Sneh,
• Takeru Torigoe and
• Yoichiro Kuninobu

Beilstein J. Org. Chem. 2021, 17, 885–890, doi:10.3762/bjoc.17.74

• (cycloalkanes and substrates bearing a benzylic C–H group). Therefore, there remains room for the development of a simple manganese catalytic system to achieve C(sp3)−H halogenation using commercially available reagents. Herein, we report a manganese-catalyzed C(sp3)–H bromination reaction at the methine and

Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols

• Emine Salamci and
• Yunus Zozik

Beilstein J. Org. Chem. 2021, 17, 705–710, doi:10.3762/bjoc.17.59

• have become important structural components for drug development with a modifying action as inhibitors of glycosidases [4][5][6][7][8][9][10]. Aminocyclitols are amino polyhydroxy cycloalkanes [2] formally derived from cyclitols [11][12][13][14][15], which are polyhydroxylated cycloalkanes, via

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• temperatures are involved, and the reaction requires relatively longer times compared to the organometallic route. Reaction of metal phosphides with cycloalkanes Cyclopropane easily undergoes nucleophilic substitution reactions because of its high ring strain. Tan et al. [69] reported the preparation of 9-(2

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• air at room temperature and presents a predictable reactivity pattern as well as a wide functional group tolerance. The substrate scope was evaluated on 33 styrenes, β-substituted styrenes, heteroaromatic olefins and vinyl cycloalkanes (Scheme 4). The trifluoromethyl radical was generated from

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

•  11). Conclusion In conclusion, the chemical behavior of the alcoholic functions of some vicinal diol derivatives towards fluorination has been investigated under various conditions. The fluorination reactions of the highly functionalized cycloalkanes were found to be highly substrate dependent

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

Unusual traits of cis and trans-2,3-dibromo-1,1-dimethylindane on the way from 1,1-dimethylindene to 2-bromo-, 3-bromo-, and 2,3-dibromo-1,1-dimethylindene

• Rudolf Knorr,
• David S. Stephenson,
• Ernst Lattke,
• Petra Böhrer and
• Jakob Ruhdorfer

Beilstein J. Org. Chem. 2016, 12, 1178–1184, doi:10.3762/bjoc.12.113

• interchange reaction of 7 in hexane as the solvent with n-butyllithium (n-BuLi) ocurred predominantly at the 3-position of 7 with formation of 2-bromo-3-lithio-1,1-dimethylindene (10, Scheme 3). In the absence of cycloalkanes or benzene from the hydrocarbon solvent, rather concentrated mixtures of 7 and n

Enantioselective carbenoid insertion into C(sp³)–H bonds

• J. V. Santiago and
• A. H. L. Machado

Beilstein J. Org. Chem. 2016, 12, 882–902, doi:10.3762/bjoc.12.87

• asymmetric carbon configuration. Carbenoid insertion into a C(sp3)–H bond as the key step of the Taber’s (+)-α-cuparenone (8) synthesis. First enantioselective carbenoid insertion into C–O bonds catalyzed by chiral metallic complexes. Asymmetric carbenoid insertions into C(sp3)–H bonds of cycloalkanes

Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H)-ones and isoquinoline-1,3(2H,4H)-diones

• Ping Qian,
• Bingnan Du,
• Wei Jiao,
• Haibo Mei,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2016, 12, 301–308, doi:10.3762/bjoc.12.32

• [18][19], decarboxylative alkenylation of cycloalkanes with aryl vinylic carboxylic acids [20][21], trifluoromethylthiolation [22], thiolation [23][24], alkenylation [25][26], dehydrogenation−olefination and esterification [27][28], radical addition/1,2-aryl migration [29], cascade alkylation

• unactivated cycloalkanes (instead of alcohols) could act as radical partners for this system. However, the reaction gave a complex mixture with 15% chemical yield of the expected product (Scheme 1c). Fortunately, when a methyl substituent was introduced onto the C–C double bond of the N-allylbenzamide

• cycloalkanes 2 and N-methyl-N-(2-methylallyl)benzamide (4a). As indicated in Scheme 3, several cycloalkanes were well-tolerated in this radical reaction resulting in the corresponding product. In the case of cyclopentane (2b), a slightly lower chemical yield was obtained (46%, 5ab), while the reactions of

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• a catalytic system consisting of (BPMED)CuI (copper(I) bisimine complex), N-hydroxyphthalimide (NHPI), KB(C6F5)4 and KI. The protocol allowed the selective fluorination of various substrates, including cycloalkanes and benzylic compounds using commercially available Selectfluor as fluorine source

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• -immobilized manganese phthalocyanine/H2O2aq [166], a Ni(II) complex/H2O2aq [167], and ZnBr2/H2O2 [168]. The oxidative C–O coupling of aromatic aldehydes 181 with cycloalkanes 182 was accomplished in the presence of the Cu(OAc)2/t-BuOOH system to prepare products 183. This reaction is unusual in that it

• inert CH-reagents, cycloalkanes, to form a product, which can be subjected to higher oxidation under the conditions of oxidative coupling (Scheme 38). Related oxidative C–O coupling reactions of alkanes with methylarenes and carboxylic acids are discussed in sections 4.1 and 6, respectively. Different

Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinyl carboxylic acids via a radical process

• Jincan Zhao,
• Hong Fang,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2013, 9, 1718–1723, doi:10.3762/bjoc.9.197

• (acac)3-catalyzed decarboxylative coupling of 2-(aryl)vinyl carboxylic acids with cycloalkanes was developed by using DTBP as an oxidant through a radical process. This reaction tolerates a wide range of substrates, and products are obtained in good to excellent yields (71–95%). The reaction also shows

• excellent stereoselectivity, and only trans-isomers are obtained. Keywords: alkenylation; cycloalkanes; decarboxylative; Fe(acac)3; free radical; sp3 C–H bonds; Introduction Direct C–H functionalization has become one of the most useful and attractive tools in organic chemistry because it can construct

• alkenylation of cycloalkanes with high selectivity and stereospecificity remains a great challenge and attracted a lot of attention in the past years. In 1996, the Fuchs group described the alkenylation of cyclohexane by a radical reaction with vinyl triflone [58]. In 2003, the Yao group reported that styryl

ML212: A small-molecule probe for investigating fluconazole resistance mechanisms in Candida albicans

• Willmen Youngsaye,
• Cathy L. Hartland,
• Barbara J. Morgan,
• Amal Ting,
• Partha P. Nag,
• Benjamin Vincent,
• Carrie A. Mosher,
• Joshua A. Bittker,
• Sivaraman Dandapani,
• Michelle Palmer,
• Luke Whitesell,
• Susan Lindquist,
• Stuart L. Schreiber and
• Benito Munoz

Beilstein J. Org. Chem. 2013, 9, 1501–1507, doi:10.3762/bjoc.9.171

• proceeded to evaluate the SAR of the C3 substituent next (Table 2). Removal of the original benzene ring produces the inactive analogue 21. Similarly, installing acyclic alkyl systems such as an ethyl (22) or tert-butyl group (23) does not yield active compounds. Proceeding to cycloalkanes, a SAR trend

Directed aromatic functionalization

• Victor Snieckus

Beilstein J. Org. Chem. 2011, 7, 1215–1218, doi:10.3762/bjoc.7.141

• chemistry [53] requires supplementary contemporary synthetic work in order to vigorously test its viability. The prospect of metal-catalyzed dehydrogenative conversion of cycloalkanes to aromatics as new source of aromatic feedstocks is also on the immediate horizon [54]. In this Thematic Series, you will

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

• Magnus Rueping and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2010, 6, No. 6, doi:10.3762/bjoc.6.6

• . Furthermore, an efficient intramolecular variant of this procedure starting from biaryl benzyl alcohol 23 led to substituted fluorenes 24 which have shown to be valuable scaffolds for blue light emitting polymers (Scheme 11A) [46]. A similar route to fluorenes and other annulated cycloalkanes 26 was