Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

• Thaipparambil Aneeja,
• Cheriya Mukkolakkal Abdulla Afsina,
• Padinjare Veetil Saranya and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 37–52, doi:10.3762/bjoc.18.4

• , carboxylic acids, tetrazoles, aldehydes, amidines, and amides [7][8][9][10][11]. This has been suitably transformed into structurally diverse and complex molecules. In 1927, Pongratz reported a method towards cyanation reactions [12]. From then, onwards, cyanation gained prime focus and achieved much

• trimethylsilyl cyanide (TMSCN) in acetonitrile solvent under CFL light irradiation. 4 Miscellaneous An efficient methodology for the synthesis of α-aminonitriles via the one-pot coupling of aldehydes, amines and trimethylsilyl cyanide was reported [46]. This reaction was catalyzed by RuCl3 and used acetonitrile

• as solvent (Scheme 23). Both aromatic and aliphatic aldehydes performed well and gave the desired products in good yields. At the same time ketones were found less active in this strategy. The operational simplicity and high yield of products are the prominent characteristics of this reaction. In

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• HAT step energetics and determined an optimized geometry for the transition state, showing that the hydrogen atom transfer between aldehydes and DABCO is a mildly endergonic, yet sufficiently fast step. The same calculations were performed with quinuclidine, for comparison of both catalysts and the

• functionalization using DABCO as a hydrogen atom abstractor in a photocatalytic strategy for synthetic purposes. In this context, our work aims to broaden the scope of DABCO-promoted photocatalytic C–H functionalization including formyl bonds of aldehydes as substrates (Figure 2e). The acyl radicals generated

• optimized reaction conditions. Also, when other aldehydes or aryl bromides were tested in the absence of DABCO, a very strong dependence on the aryl bromide electronics emerged, leading to diminished yields, remarkably for electron-rich aryl bromides (Table 1, entry 10 and Supporting Information File 1

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

• aliphatic nitriles explored, the reaction further demonstrated the synthetic potential of C(sp3)–H species within CDC methodology. In 2013, the Li group established a carbonyl-arylation of N-arylacrylamides 60 with alkyl and aryl aldehydes 65 (Scheme 11) [83]. Like Li’s report in 2013 (Scheme 10) [80], the

• cyclization with the aryl ring constructs the 6-membered heterocyclic framework. In 2015, the Li group investigated the radical addition/cyclization of olefinic malonate and β-diketone compounds 96 with aldehydes 97 (Scheme 19) [97]. The reaction was feasible with ketones; however, lower product yields were

• applicability in late-stage functionalization. The Bao group has since demonstrated many other carbon-centered radicals were amenable in the carboazidation reaction of alkenes including diacylperoxides [133] and aldehydes [134]. In 2021, the Bao group followed up on their previous work and developed an

Photophysical, photostability, and ROS generation properties of new trifluoromethylated quinoline-phenol Schiff bases

• Inaiá O. Rocha,
• Yuri G. Kappenberg,
• Wilian C. Rosa,
• Clarissa P. Frizzo,
• Nilo Zanatta,
• Marcos A. P. Martins,
• Isadora Tisoco,
• Bernardo A. Iglesias and
• Helio G. Bonacorso

Beilstein J. Org. Chem. 2021, 17, 2799–2811, doi:10.3762/bjoc.17.191

• Schiff bases 3bb–be with 40–89% yield for the isolated products after recrystallization from ethanol (Scheme 3). With some exceptions, electron-deficient or electron-rich substituted 2-aryl-6-aminoquinolines and aromatic aldehydes worked very well to furnish the Schiff bases 3. However, a poor yield (20

The PIFA-initiated oxidative cyclization of 2-(3-butenyl)quinazolin-4(3H)-ones – an efficient approach to 1-(hydroxymethyl)-2,3-dihydropyrrolo[1,2-a]quinazolin-5(1H)-ones

• Alla I. Vaskevych,
• Nataliia O. Savinchuk,
• Ruslan I. Vaskevych,
• Eduard B. Rusanov,
• Oleksandr O. Grygorenko and
• Mykhailo V. Vovk

Beilstein J. Org. Chem. 2021, 17, 2787–2794, doi:10.3762/bjoc.17.189

• halogenoketones or ketocarboxylic acids upon action of SnCl2·H2O, TiCl4/Zn, or Fe/CH3COOH can be mentioned [28][29][30]. 1-Aryl-substituted tetrahydropyrrolo[1,2-a]quinazolin-5-ones can be also obtained by a Brønsted acid-catalyzed annulation of arylcyclopropane aldehydes and N′-anthranilic hydrazides [31], as

Me₃Al-mediated domino nucleophilic addition/intramolecular cyclisation of 2-(2-oxo-2-phenylethyl)benzonitriles with amines; a convenient approach for the synthesis of substituted 1-aminoisoquinolines

• Krishna M. S. Adusumalli,
• Lakshmi N. S. Konidena,
• Hima B. Gandham,
• Krishnaiah Kumari,
• Krishna R. Valluru,
• Satya K. R. Nidasanametla,
• Venkateswara R. Battula and
• Hari K. Namballa

Beilstein J. Org. Chem. 2021, 17, 2765–2772, doi:10.3762/bjoc.17.186

• cycloaddition reactions and also serves as a precursor for the generation of important functional groups like amines, aldehydes, ketones and carboxylic acids. Even though the nitrile functional group is prevalent in the transformation into different functional groups, the synthetic approaches that incorporate

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• (Figure 3). Chemical approaches Modified sugar rings containing a sulfur heteroatom at C-3' are found in medicinal chemistry. The reaction between oxygen-containing substrates (such as aldehydes or acetals) and sulfur sources (such as thiols or sulfenyl compounds) is one of the most important methods to

Synthesis of highly substituted fluorenones via metal-free TBHP-promoted oxidative cyclization of 2-(aminomethyl)biphenyls. Application to the total synthesis of nobilone

• Ilya A. P. Jourjine,
• Lukas Zeisel,
• Jürgen Krauß and
• Franz Bracher

Beilstein J. Org. Chem. 2021, 17, 2668–2679, doi:10.3762/bjoc.17.181

• give imines, iminium salts, aldehydes and other, in some cases dimeric products [49]. Here, oxidation of the benzylic amino moiety should lead either to iminium ions (or N-acyl iminium ions) 4a as strong electrophiles or to stabilized radicals 4b which could undergo cyclization to give the fluorenone

• ) in 22%, 60% and 26% yield, respectively (Table 1, entries 1, 11 and 12, all under conditions b). This leads us to the conclusion that, different from aldehydes, the success of the cyclization for amines is highly dependent on the solvent in which TBHP is dissolved, indicating that water may have a

• of biaryl aldehyde intermediates 8, reduction [60] in the case of nitriles 14, or Boc deprotection [61] for 14k, m, o according to standard protocols (Schemes 4–7; for details, see Supporting Information File 1). Although it may seem counterintuitive to first convert aldehydes 8 and nitriles 14 into

N-Sulfinylpyrrolidine-containing ureas and thioureas as bifunctional organocatalysts

• Viera Poláčková,
• Dominika Krištofíková,
• Boglárka Némethová,
• Renata Górová,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2021, 17, 2629–2641, doi:10.3762/bjoc.17.176

• Michael additions of aldehydes to nitroalkenes both under solvent-free conditions and in solution. The N-sulfinylurea catalyst was more efficient than the corresponding thiourea. For some substrates, enantioselectivities reached 98% ee. The stereogenic center on the sulfur did not have a considerable

• aldehydes and hydrogen-bond activation of nitroalkenes. Keywords: asymmetric organocatalysis; hydrogen bond; Michael addition; pyrrolidine; thiourea; urea; Introduction Asymmetric organocatalysis became one of the strategic ways for the efficient synthesis of chiral compounds [1]. Bifunctional catalysis

• organocatalytic transformations were successfully performed under solvent-free ball-milling conditions [30][31]. In this context, we describe the synthesis of new pyrrolidine appended sulfinylurea and thiourea organocatalysts and their assessment in Michael additions of aldehydes to nitroalkenes. Furthermore, we

Recent advances in organocatalytic asymmetric aza-Michael reactions of amines and amides

• Pratibha Sharma,
• Raakhi Gupta and
• Raj K. Bansal

Beilstein J. Org. Chem. 2021, 17, 2585–2610, doi:10.3762/bjoc.17.173

• 108 to aliphatic α,β-unsaturated aldehydes 109 and synthesized biologically active acyclonucleoside 110 via an iminium-ion activation mechanism. The initially formed product was reduced in situ to afford the final product in 82–89% yield and 89–96% ee (Table 25) [66]. In a similar method, Joie et al

• . accomplished an asymmetric organocatalytic quadruple cascade reaction of various α-ketoamides 111 with aromatic α,β-unsaturated aldehydes 112 to obtain tetraaryl-substituted 2-azabicyclo[3.3.0]octadienones 114 in good yields (34–71%) with excellent diastereo- and enantioselectivities (84–97%). The reaction

• -unsaturated aldehydes. Asymmetric aza-Michael organocatalytic quadruple cascade reaction. Asymmetric synthesis of chiral 4-naphthylquinoline-3-carbaldehydes. Funding The authors express gratitude to the authorities of the IIS (deemed to be University), Jaipur, India for providing the necessary research

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

• Scott Benz and
• Andrew S. Murkin

Beilstein J. Org. Chem. 2021, 17, 2570–2584, doi:10.3762/bjoc.17.172

• use of aldehydes (R′ = H), which are usually less stable than their ketone counterparts; (2) ring expansion (Z, R = cyclic) or contraction (Z, R′ = cyclic) of strained cyclic α-ketols; (3) the use of α-dicarbonyl compounds (R′ = acyl, ester, amide, etc.), which lead to more stable β-dicarbonyl

Synthesis of new substituted 7,12-dihydro-6,12-methanodibenzo[c,f]azocine-5-carboxylic acids containing a tetracyclic tetrahydroisoquinoline core structure

• Agnieszka Grajewska,
• Maria Chrzanowska and
• Wiktoria Adamska

Beilstein J. Org. Chem. 2021, 17, 2511–2519, doi:10.3762/bjoc.17.168

• diethyl acetal (11) to give 12 with 73% yield. Additionally, the aminoacetal 12 was also synthesized via another route involving a double reductive amination of the aldehydes 2a and 2f with aminoacetaldehyde acetal (1) with 59% yield. The aminoacetal 12 was then treated with 4% HCl in THF at reflux but in

Recent advances in the tandem annulation of 1,3-enynes to functionalized pyridine and pyrrole derivatives

• Yi Liu,
• Puying Luo,
• Yang Fu,
• Tianxin Hao,
• Xuan Liu,
• Qiuping Ding and
• Yiyuan Peng

Beilstein J. Org. Chem. 2021, 17, 2462–2476, doi:10.3762/bjoc.17.163

• annulation of 2-en-4-ynyl azides 1 could provide the corresponding 3,6-disubstituted pyridines 2 in 60–88% yield in the presence of TFA (2.0 equiv). The reaction substrates, 2-en-4-ynyl azides 1, derived from MBH acetates of acetylenic aldehydes, could tolerate various substituted aryl, indolyl, and alkyl

Enantioselective PCCP Brønsted acid-catalyzed aminalization of aldehydes

• Martin Kamlar,
• Robert Reiberger,
• Martin Nigríni,
• Ivana Císařová and
• Jan Veselý

Beilstein J. Org. Chem. 2021, 17, 2433–2440, doi:10.3762/bjoc.17.160

• Abstract Here we present an enantioselective aminalization of aldehydes catalyzed by Brønsted acids based on pentacarboxycyclopentadienes (PCCPs). The cyclization reaction using readily available anthranilamides as building blocks provides access to valuable 2,3-dihydroquinazolinones containing one

• organocatalytic synthesis of molecules with this moiety uses the reaction between aldehydes and anthranilamide building blocks. The advantage of this methodology lies in the fact that both starting materials are readily available, and the enantioselectivity of such cyclization reactions can be controlled by

• -workers, using an (S)-TRIP derivative as the chiral catalyst (Figure 1) [14]. Soon after, Rueping et al. developed a similar methodology catalyzed by other chiral BINOL-phosphoric acids [15]. However, the reaction suffered from limited scope to aromatic aldehydes without an ortho-substitution; the

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

• gives compound 45 along with the unexpected product 46 (Scheme 17) [63]. Later they had reported the reaction between alkenyl hydroperoxide 47 and aldehydes 48 to form hemiperoxyacetal 49 which subsequently reacted with Hg(OAc)2 and a catalytic amount of perchloric acid (HClO4) forming cyclized product

• -propargyl glycolaldehyde dithioacetals 107 via their dithioketals and dithioacetals to synthesize six-membered heterocycles 108 and 109 (Scheme 32). Five-membered dihydrofuryl aldehydes were also isolated as minor products in some examples. Following a similar protocol, Biswas et al. later published the

Synthesis of phenanthridines via a novel photochemically-mediated cyclization and application to the synthesis of triphaeridine

• Songeziwe Ntsimango,
• Kennedy J. Ngwira,
• Moira L. Bode and
• Charles B. de Koning

Beilstein J. Org. Chem. 2021, 17, 2340–2347, doi:10.3762/bjoc.17.152

• –Miyaura cross-coupling reaction of a variety of halogenated methoxybenzene-containing compounds with 2-(formylphenyl)boronic acids in generally good yields [15]. As a next step, the biaryl aldehydes 13a–f were converted into their corresponding oximes 14a–f in good yields as a mixture of (E) and (Z

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• heterolytic cleavage of HCl as displayed in Scheme 7 [55]. Moreover, other catalysts with amine functional groups were found more efficient in the enantioselective α-alkylation of aldehydes (Scheme 10b) [48] or in the asymmetric Mannich synthesis of α-amino esters using Takemoto’s bifunctional catalyst 44 [67

• catalyzed by chiral squaramide 37 by Jacobsen et al. Bis-urea-catalyzed enantioselective fluorination of a) β-bromosulfides and b) β-haloamines by Gouverneur et al. a) Bifunctional thiourea anion-binding – basic/nucleophilic catalysts. Selected applications in b) enantioselective α-alkylation of aldehydes

• aromatic aldehydes under weakly acidic conditions. Anion-binding catalyst development in the enantioselective addition of silyl ketene acetals to 1-chloroisochromane (73). Limiting factors and influences on catalyst activation and anion abstraction. a) Macrocyclic bis-thiourea catalyst in a

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• -mediated C(sp3)–H functionalizations [53][54], the MacMillan group reported a photoredox nickel-catalyzed aldehyde C–H arylation, vinylation, or alkylation [129]. The ketone-forming reaction was conveniently realized by the reaction of aldehydes 89 with aryl, alkenyl, or alkyl bromides in the presence of

Transition-metal-free intramolecular Friedel–Crafts reaction by alkene activation: A method for the synthesis of some novel xanthene derivatives

• Tülay Yıldız,
• İrem Baştaş and
• Hatice Başpınar Küçük

Beilstein J. Org. Chem. 2021, 17, 2203–2208, doi:10.3762/bjoc.17.142

• of their important biological and fluorescent uses. To summarize the main syntheses of these studies: in particular, transition metal-catalyzed cascade benzylation–cyclization [17], cyclization of polycyclic aryl triflate esters [18], reaction of β-naphthol and aldehydes [19][20] or inter- or

• intramolecular coupling of arynes by aldehydes or phenols [21][22][23][24], and Lewis acid-catalyzed cyclization of salicylaldehydes and cyclohexenones or tetralones [25]. Some other new and prominent synthesis methods of xanthenes are the tandem arylation/Friedel–Crafts reaction of o-hydroxy bisbenzylic

Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)

• Tania Xavier,
• Sylvie Condon,
• Christophe Pichon,
• Erwan Le Gall and
• Marc Presset

Beilstein J. Org. Chem. 2021, 17, 2085–2094, doi:10.3762/bjoc.17.135

• widespread applications being aldol or Mannich-type addition reactions with carbonyl compounds and imines, respectively [4], and Galat olefination reactions of aldehydes [5][6][7]. Nevertheless, these developments have been mostly described with unsubstituted MAHOs, and the use of mono-substituted MAHOs

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• -cyclotrimerization reaction catalyzed by a cobalt/zinc reagent [40]. With regard to substituted anthracenes, this method consisted of a [2 + 2 + 2] cycloaddition reaction of 1,6-diynes 27 with 4-aryl-2-butyn-1-ols 28 (Scheme 6). The authors converted the resulting benzylic alcohols 29 to the corresponding aldehydes

• efficiently cyclized [42]. Friedel–Crafts alkylation of arenes with aromatic aldehydes The Lewis acid-catalyzed Friedel–Crafts alkylation of electron-rich arenes with aromatic aldehydes has proven an efficient and often direct method to prepare anthracene derivatives. Kodomari and co-workers disclosed a

• convenient synthesis of triarylmethanes and 9,10-diarylanthracenes from reactions of arenes and aromatic aldehydes by using acetyl bromide in the presence of silica gel-supported zinc bromide [43]. The methodology developed by these authors involved using excess of one of the reagents. When the authors

Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• . Catalysis via covalent bonding Organocatalysts made from chiral secondary amines have been widely used in the last years. According to Jørgensen, in general, the carbonyl functionalization employing amine catalysts can be separated in four different types [29]. When aldehydes are employed, both

• electrophilic and nucleophilic α-functionalizations are possible, whereas with the use of α,β-unsaturated aldehydes the β-position is functionalized with nucleophiles and the γ-position with electrophiles. In this sense, Jørgensen and colleagues have developed the first organocatalytic asymmetric Michael

• acid (4) as catalyst [30]. Based on this pioneer work, our research group described an efficient, highly stereoselective, one-pot process comprising an organocatalytic conjugate addition of dimedone or 4-hydroxycoumarin 1 to α,β-unsaturated aldehydes 2 followed by an intramolecular isocyanide-based

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

• heterogeneous vanadium-based catalysts have been employed to obtain alcohols and carbonyl compounds through oxidation, including VOSO4, Na(VO3), VO(acac)2, VOX3, among others. Obtaining ketones and aldehydes from hydrocarbon compounds through vanadium-mediated activation of C(sp3)–H bonds in a benzylic position

• derivatives. Using H2O2 as an oxidant agent, ketones and aldehydes were obtained from hydrocarbons with high yields (85–99%, Scheme 9B and 9C). Although the authors did not explore the biological effects of the obtained products, this class of molecules resembles the basic structure of several important

• for the allylation of aldehydes promoted by a dual catalytic system comprising CrCl3 and an iridium-based photocatalyst that was recently developed by Schwarz and co-workers [119]. Similar conditions were further employed to synthesize monoprotected 1,2-homoallylic diols from aldehydes and silyl and

Cerium-photocatalyzed aerobic oxidation of benzylic alcohols to aldehydes and ketones

• Girish Suresh Yedase,
• Sumit Kumar,
• Jessica Stahl,
• Burkhard König and
• Veera Reddy Yatham

Beilstein J. Org. Chem. 2021, 17, 1727–1732, doi:10.3762/bjoc.17.121

• , Universitätstraße 31, D-93053 Regensburg, Germany 10.3762/bjoc.17.121 Abstract We have developed a cerium-photocatalyzed aerobic oxidation of primary and secondary benzylic alcohols to aldehydes and ketones using inexpensive CeCl3·7H2O as photocatalyst and air oxygen as the terminal oxidant. Keywords: alcohol

• ; aldehydes; cerium; oxidation; ketones; visible light; Introduction The selective oxidation of alcohols to carbonyl compounds [1][2] is an important process for producing a wide range of value-added fine chemicals [3][4][5][6]. In the traditional oxidation process stoichiometric amounts of oxidants such as

• herein report a mild aerobic photocatalytic oxidation of benzylic alcohols to aldehydes and ketones using 10 mol % CeCl3·7H2O (Scheme 1). Results and Discussion A variety of reaction parameters was tested during the optimization of the reaction with 4-iodobenzyl alcohol (1a) as the model substrate and

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