Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• ) hypervalent iodonium salts, for the efficient synthesis of fluorinated sulfoxonium ylides (Scheme 1c). Results and Discussion Since the introduction of hypervalent iodonium salts in organic chemistry, these valuable reagents have led to many new strategies for carbon–carbon bond formation [31][32]. Our

Electrochemical formal homocoupling of sec-alcohols

• Kosuke Yamamoto,
• Kazuhisa Arita,
• Masashi Shiota,
• Masami Kuriyama and
• Osamu Onomura

Beilstein J. Org. Chem. 2022, 18, 1062–1069, doi:10.3762/bjoc.18.108

• electrolysis; Introduction Carbon–carbon bond formation is one of the most fundamental and important reactions in synthetic organic chemistry. Reductive coupling of carbonyl compounds known as pinacol coupling would be a powerful method to construct vic-1,2-diol scaffolds through C–C bond formation [1][2

Electroreductive coupling of 2-acylbenzoates with α,β-unsaturated carbonyl compounds: density functional theory study on product selectivity

• Naoki Kise and
• Toshihiko Sakurai

Beilstein J. Org. Chem. 2022, 18, 956–962, doi:10.3762/bjoc.18.95

• –carbon bond formation [1][2][3][4]. Recently, we reported the electroreductive coupling of phthalic anhydrides with α,β-unsaturated carbonyl compounds in the presence of chlorotrimethylsilane (TMSCl) and subsequent treatment with 1 M HCl to give 1,4-dihydroxynaphthalenes and 2-methyl-2,3

• studied using DFT calculations. Keywords: 2-acylbenzoates; chlorotrimethylsilane; 3-(3-cyanoethyl)phthalides; 2-cyanonaphthalen-1-ols; electroductive coupling; Introduction The electroreductive coupling between carbon–heteroatom and carbon–carbon double bonds is one of the promising methods for carbon

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• inductive heating technology has also been used in multistep processes targeting drugs or important molecules in the fragrance industry. The first example deals with a metal-free carbon–carbon-bond formation process between tosylhydrazones generated from the corresponding aldehydes 74 and boronic acids 76

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• exhibiting solid-state fluorescence, although the fluorescence partially disappears in solution, and there is a large shift to red and blue [98][99]. Carbon–carbon bond formation The main steps in a synthesis usually involve C–C bond formation, which is usually the main reaction step, or functional group

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• reasons of clarity, newly formed bonds are sketched in red, with newly formed cyclic structures being highlighted. Review Iron-catalyzed cross-coupling Metal-catalyzed cross-coupling reactions have become a staple for carbon–carbon bond formation. The late TMs that have dominated the field of cross

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• evidence for radical pathways involving vanadium-peroxo species [76], with a few exceptions [95]. Vanadium-based catalysts have been employed in carbon–carbon bond formation reactions, such as arene couplings, thereby proving especially useful in the synthesis of bioactive compounds, including natural

• in a cheaper way leading to an easier access of currently expensive treatments to the general population. Chromium-catalyzed C–H activation Chromium is a relatively abundant transition metal that has been used for oxidative reactions, including cross-coupling and carbon–carbon bond formation

Suzuki–Miyaura cross coupling is not an informative reaction to demonstrate the performance of new solvents

• James Sherwood

Beilstein J. Org. Chem. 2020, 16, 1001–1005, doi:10.3762/bjoc.16.89

• catalysed carbon–carbon bond formation, making it an obvious case study to validate the performance of novel solvents [1][2][3][4][5][6][7]. The polarity of the solvent is known to determine the structure and activity of catalytic intermediates, the rate determining step, and stereochemistry (where

Computational characterization of enzyme-bound thiamin diphosphate reveals a surprisingly stable tricyclic state: implications for catalysis

• Ferran Planas,
• Michael J. McLeish and
• Fahmi Himo

Beilstein J. Org. Chem. 2019, 15, 145–159, doi:10.3762/bjoc.15.15

• Abstract Thiamin diphosphate (ThDP)-dependent enzymes constitute a large class of enzymes that catalyze a diverse range of reactions. Many are involved in stereospecific carbon–carbon bond formation and, consequently, have found increasing interest and utility as chiral catalysts in various biocatalytic

Synthesis of unnatural α-amino esters using ethyl nitroacetate and condensation or cycloaddition reactions

• Glwadys Gagnot,
• Vincent Hervin,
• Eloi P. Coutant,
• Sarah Desmons,
• Racha Baatallah,
• Victor Monnot and
• Yves L. Janin

Beilstein J. Org. Chem. 2018, 14, 2846–2852, doi:10.3762/bjoc.14.263

• another approach involving an oxidative addition of ethyl nitroacetate (4) on the methylene-bearing dipolarophiles 25 mediated by cerium(IV) ammonium nitrate (CAN). This was inspired by reports describing CAN-mediated carbon–carbon bond formation reactions between ethyl nitroacetate (4) and tri-O

A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations

• Andrew Kenny,
• Alba Pisarello,
• Arron Bird,
• Paula G. Chirila,
• Alex Hamilton and
• Christopher J. Whiteoak

Beilstein J. Org. Chem. 2018, 14, 2366–2374, doi:10.3762/bjoc.14.212

• of the acetic acid for 3-buten-2-one is energetically unfavourable (≈9 kcal mol−1), which differs significantly from the benzamide functionalisation example, where the substitution if favoured (Figure 2). The carbon–carbon bond formation step, functionalisation of the aromatic ring, proceeds with a

Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer

• Xiaoshen Ma and
• Seth B. Herzon

Beilstein J. Org. Chem. 2018, 14, 2259–2265, doi:10.3762/bjoc.14.201

• –X addition, X = O [5][6][7][8][9], I [3], Br [3], Se [3], S [8][9][10], Cl [8][11], F [12][13], and N [8][14][15][16][17]) by metal-mediated hydrogen atom transfer (HAT) [18][19][20][21] are now known. Additionally, methods to achieve carbon–carbon bond formation to alkenes by HAT have been

• –carbon bond formation strategies were also examined using the Co(acac)2 HAT system. Sulfonyl oximes 6a and 6b [32] afforded the carbon–carbon coupled products 4j and 4k in 60% and 48% yields, respectively (Table 1, entries 11 and 12, respectively). Recently, our laboratory reported a formal

• bearing nitro substituents were not compatible with this HAT coupling. For example, the use of p-nitrobenzendiazonium tetrafluoroborate failed to provide the expected coupling product 7l. This may be due to alternative reaction pathways involving reduction of the nitro substituent [17]. Additional carbon

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst

• Kimihiro Komeyama,
• Shunsuke Sakiyama,
• Kento Iwashita,
• Itaru Osaka and
• Ken Takaki

Beilstein J. Org. Chem. 2018, 14, 1413–1420, doi:10.3762/bjoc.14.118

• ; Introduction Carbon–carbon bond formation is the fundamental and central transformation of synthetic organic chemistry. The elaboration and extension of a carbon framework via a series of carbon–carbon bond-forming reactions are extremely important for medicinal chemistry and agrochemical and natural product

Stereoselective nucleophilic addition reactions to cyclic N-acyliminium ions using the indirect cation pool method: Elucidation of stereoselectivity by spectroscopic conformational analysis and DFT calculations

• Koichi Mitsudo,
• Junya Yamamoto,
• Tomoya Akagi,
• Atsuhiro Yamashita,
• Masahiro Haisa,
• Kazuki Yoshioka,
• Hiroki Mandai,
• Koji Ueoka,
• Christian Hempel,
• Jun-ichi Yoshida and
• Seiji Suga

Beilstein J. Org. Chem. 2018, 14, 1192–1202, doi:10.3762/bjoc.14.100

• physiological and pharmacological activities [1][2][3]. As many of these compounds feature asymmetric carbon atoms at the α-position of the cyclic amine, the stereoselective carbon–carbon bond formation at this position is of great importance from the perspective of drug discovery [4][5]. Meanwhile the “cation

• very efficiently yield carbon–carbon bond-formation products. In addition, this research lead to the development of an indirect cation pool method that enables the creation of the cation pool by reacting a cation precursor having a C–S bond with an electrochemically generated ArS(ArSSAr)+ as the cation

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

• Takeshi Fujita,
• Ryo Kinoshita,
• Tsuyoshi Takanohashi,
• Naoto Suzuki and
• Junji Ichikawa

Beilstein J. Org. Chem. 2017, 13, 2682–2689, doi:10.3762/bjoc.13.266

• site-selective intramolecular iodoarylation by the appropriate cationic iodine species. Iodoarylation of 2-(2-aryl-3,3-difluoroallyl)biaryls proceeded via regioselective carbon–carbon bond formation at the carbon atoms in β-position to the fluorine substituents, thereby constructing dibenzo-fused six

Conjugated nitrosoalkenes as Michael acceptors in carbon–carbon bond forming reactions: a review and perspective

• Yaroslav D. Boyko,
• Valentin S. Dorokhov,
• Alexey Yu. Sukhorukov and
• Sema L. Ioffe

Beilstein J. Org. Chem. 2017, 13, 2214–2234, doi:10.3762/bjoc.13.220

• particular focus on recent developments in this methodology and its use in total synthesis. Keywords: carbon–carbon bond formation; Michael addition; nitrosoalkenes; oximes; total synthesis; Introduction Conjugated nitrosoalkenes (NSA) are close analogs of α-nitroalkenes, which are important Michael

• exploited the Michael addition of enolates to nitrosoalkenes in their studies towards syntheses of 3-methoxy-9β-estra(1,3,5(10))trien(11,17)dione (25) (1977) [31] and (+/−)-isocomene (1981) [32]. The key carbon–carbon bond formation step in the synthesis of steroid 25 was the stereoselective reaction of α

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

• Abdusalom A. Suleymanov,
• Dmitry V. Vasilyev,
• Valentin V. Novikov,
• Yulia V. Nelyubina and
• Dmitry S. Perekalin

Beilstein J. Org. Chem. 2017, 13, 639–643, doi:10.3762/bjoc.13.62

• /phosphine ligand/Zn/ZnI2 for the carbon–carbon bond formation has become a subject of a growing interest (for reviews see [15][16][17][18][19][20][21]). This catalytic system has many advantages, including the availability of the cobalt salts and high tolerance to organic functional groups (for some recent

Chromium(II)-catalyzed enantioselective arylation of ketones

• Gang Wang,
• Shutao Sun,
• Ying Mao,
• Zhiyu Xie and
• Lei Liu

Beilstein J. Org. Chem. 2016, 12, 2771–2775, doi:10.3762/bjoc.12.275

• ; asymmetric catalysis; chromium; ketone; tertiary alcohol; Introduction Catalytic enantioselective carbon–carbon bond formation reactions have achieved enormous development during the last few decades as a consequence of the growing demand for enantiopure compounds in modern industry, especially the

Chiral ammonium betaine-catalyzed asymmetric Mannich-type reaction of oxindoles

• Masahiro Torii,
• Kohsuke Kato,
• Daisuke Uraguchi and
• Takashi Ooi

Beilstein J. Org. Chem. 2016, 12, 2099–2103, doi:10.3762/bjoc.12.199

• efficient construction of vicinal quaternary and tertiary stereocenters [9][10][11][12][13][14][15][16][17][18][19][20][21][22]. In particular, the application of 3-aryl substituted oxindoles seems problematic; hence, the full potential of this useful carbon–carbon bond formation is yet to be realized [12

Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene

• Frederick J. Seidl and
• Noah Z. Burns

Beilstein J. Org. Chem. 2016, 12, 1361–1365, doi:10.3762/bjoc.12.129

• success in the copper-catalyzed cross coupling of an analogous dichlorotriflate [9], in our hands 2 failed to engage in productive carbon–carbon bond formation. An alternative retrosynthesis traced 1 back to bromochloroaldehyde 3, which should readily engage in standard olefination reactions. As 3 could

Cyclisation mechanisms in the biosynthesis of ribosomally synthesised and post-translationally modified peptides

• Andrew W. Truman

Beilstein J. Org. Chem. 2016, 12, 1250–1268, doi:10.3762/bjoc.12.120

• the RiPP, as they fundamentally change the shape of a molecule, which can be critical for receptor binding or for protection from proteolysis. Examples include amide bonds, heterocyclisation to form thiazolines or oxazolines [24] (Figure 2), oxidative carbon–carbon bond formation [25] and thioether

• -catalysed formation of thioethers in the biosynthesis of subtilosin. The mechanism for deoxyadenosine radical formation is consistent throughout most radical SAM enzymes. B) Mechanism of carbon–carbon cross-linking in streptide biosynthesis. C) Proposed carbon–carbon bond formation by SPASM protein PqqE in

Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes

• M. Emin Cinar,
• Bernward Engelen,
• Martin Panthöfer,
• Hans-Jörg Deiseroth,
• Jens Schlirf and
• Michael Schmittel

Beilstein J. Org. Chem. 2016, 12, 813–824, doi:10.3762/bjoc.12.80

• ; domino aldol; metal enolate; tetrahydropyran; Introduction Since its discovery in the late nineteenth century the aldol reaction has become one of the most powerful tools in the field of carbon–carbon bond formation [1][2][3][4][5]. It is widely used in the formation of many natural products [6][7][8][9

A new approach to ferrocene derived alkenes via copper-catalyzed olefination

• Vasily M. Muzalevskiy,
• Aleksei V. Shastin,
• Alexandra D. Demidovich,
• Namiq G. Shikhaliev,
• Abel M. Magerramov,
• Victor N. Khrustalev,
• Rustem D. Rakhimov,
• Sergey Z. Vatsadze and
• Valentine G. Nenajdenko

Beilstein J. Org. Chem. 2015, 11, 2072–2078, doi:10.3762/bjoc.11.223

• –Fuchs reaction) using a 2–4-fold molar excess of triphenylphosphine [27][28][29][30][31]. Results and Discussion Synthesis of halovinylferrocenes A few years ago we discovered a new reaction for a double carbon–carbon bond formation – the reaction of catalytic olefination. It was shown that the copper

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation

• Vadim V. Bardin,
• Anton Yu. Shabalin and
• Nicolay Yu. Adonin

Beilstein J. Org. Chem. 2015, 11, 608–616, doi:10.3762/bjoc.11.68

• with C-electrophiles (Suzuki–Miyaura reaction) is one of the most intensively studied processes of the carbon–carbon bond formation. Organoboronic acids, their esters and organotrifluoroborates are partners in these reactions and the choice of the desired reagent depends on the specific requirements in

Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

• Philipp Röse,
• Steffen Emge,
• Jun-ichi Yoshida and
• Gerhard Hilt

Beilstein J. Org. Chem. 2015, 11, 174–183, doi:10.3762/bjoc.11.18

• reaction has been described where the carbon–carbon bond formation, either at the terminal carbon of the double bond (C1) or on C2 was formed, depending on the ligand system applied [5][6]. Besides the ozonolysis of the 1,4-dienes for the generation of 1,3-dicarbonyl derivatives [7][8][9], these 1,4-dienes

• -dienols could be generated from simple 1,3-dienes, such as 1,3-butadiene or 1-aryl-substituted 1,3-dienes 1, and TMS-protected allylic alcohol (Scheme 1) for the synthesis of 1,4-dienols of type 2. The cobalt-catalysed hydrovinylation reaction is highly regiospecific for the carbon–carbon bond formation

• regioisomeric products 2n and 2o were formed in good yields and acceptable regioselectivity, with the carbon–carbon bond formation taking place predominantly at the lower substituted end of the 1,3-diene moiety. These results demonstrate that the cobalt-catalysed hydrovinylation reaction is a powerful tool for