Morpholine-mediated defluorinative cycloaddition of gem-difluoroalkenes and organic azides

• Tzu-Yu Huang,
• Mario Djugovski,
• Sweta Adhikari,
• Destinee L. Manning and
• Sudeshna Roy

Beilstein J. Org. Chem. 2023, 19, 1545–1554, doi:10.3762/bjoc.19.111

• with an organic azide. A relatively wide range of 1,4,5-trisubstituted-1,2,3-triazoles was obtained in 30–70% yields with high regioselectivity and modest functional group tolerability. This work demonstrates that gem-difluoroalkenes can serve as versatile fluorinated building blocks in lieu of alkynes

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• -catalyzed version can generally be executed at room temperature and it affords exclusively 1,4-disubstituted 1,2,3-triazole derivatives, thus allowing a controlled and highly efficient connection of a variety of molecular building blocks. This “Lego-approach” found countless applications and the bestowal of

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• prior to terminal alkylation could provide a straightforward entry to trisubstituted 3-iodoindoles, which are valuable building blocks for accessing highly decorated (aza)indoles (Scheme 1). Here, we report the concise consecutive four-component synthesis of trisubstituted 3-iodoindoles. Results and

• N-iodosuccinimide prior to N-alkylation to give substituted 3-iodoindoles in a concise consecutive four-component fashion in modest to good yields. These target compounds are versatile building blocks for instance for a Suzuki coupling to give 1-alkyl-2,3-diarylindoles that can be of particular

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• ; Introduction Acyloins (also known as α-hydroxy ketones) are widely found as structural motif in natural products [1][2][3][4][5][6][7] and bioactive molecules [8][9][10][11] (Figure 1). They can also be used as building blocks in organic synthesis [12][13][14], involved in numerous transformations to other

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• ). The review of Lemaire et al., dedicated to the synthesis of glycerol ether, is complemental to this review article [57]. Of note, the review of Godfroid and Braquet attempted to decipher the binding site of PAF via a QSAR study [58]. 1.1 Synthesis of PAF and some building blocks The platelet

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

• are widespread as essential building blocks in various drugs, natural products, agrochemicals, and materials. Modern economy requires developing green strategies with improved efficiency and reduction of waste. Due to its atom and step-economy, the cross-dehydrogenative coupling (CDC) reaction has

• CDC reaction to be a new generation method for the construction of C–C bonds and it has received extensive attention and in-depth research [16][17][18][19][20][21][22][23][24]. The building blocks of ethers are widely found in biomass, chemical feedstocks, biologically active drugs, and natural

Acetaldehyde in the Enders triple cascade reaction via acetaldehyde dimethyl acetal

• Alessandro Brusa,
• Debora Iapadre,
• Maria Edith Casacchia,
• Alessio Carioscia,
• Giuliana Giorgianni,
• Giandomenico Magagnano,
• Fabio Pesciaioli and
• Armando Carlone

Beilstein J. Org. Chem. 2023, 19, 1243–1250, doi:10.3762/bjoc.19.92

• condensation coproducts, such as water, hydrogen chloride or other small molecules [1][2][3]. MCRs have a great advantage over the classical two-component reactions; they allow the construction of complex molecular motifs in only one synthetic operational step starting from simpler building blocks. For this

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• methodologies for diverse spirooxindoles have become one of the hottest research fields in organic and pharmaceutical chemistry [10][11]. In order to synthesize diverse spirooxindole derivatives, commercially available isatins and easily obtainable 3-methyleneoxindolines were the most employed building blocks

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Linker, loading, and reaction scale influence automated glycan assembly

• Marlene C. S. Dal Colle,
• Manuel G. Ricardo,
• Nives Hribernik,
• José Danglad-Flores,
• Peter H. Seeberger and
• Martina Delbianco

Beilstein J. Org. Chem. 2023, 19, 1015–1020, doi:10.3762/bjoc.19.77

• purification steps. Keywords: automated glycan assembly; photocleavable linker; polysaccharides; solid-phase synthesis; Introduction Automated glycan assembly (AGA) is a solid-phase method that enables the rapid synthesis of complex oligo- and polysaccharides from protected monosaccharide building blocks

Intermediates and shunt products of massiliachelin biosynthesis in Massilia sp. NR 4-1

• Till Steinmetz,
• Blaise Kimbadi Lombe and
• Markus Nett

Beilstein J. Org. Chem. 2023, 19, 909–917, doi:10.3762/bjoc.19.69

• ] and the photoxenobactins [32]. A unifying theme in the biosynthesis of these natural products is the use of a thiotemplate-based assembly strategy [33]. The molecular building blocks that are needed for the biosynthesis are covalently bound via thioester bonds to multi-domain enzymes. The domains

• fulfill specific functions, ranging from the selection and linkage of building blocks to their chemical modification. A plausible scenario for the formation of compounds 1–6 involves the enzymatic machinery for massiliachelin biosynthesis, namely the protein RS02200 [18]. According to our proposal (Figure

Cyclodextrins as building blocks for new materials

• Miriana Kfoury and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2023, 19, 889–891, doi:10.3762/bjoc.19.66

• Miriana Kfoury Sophie Fourmentin Université du Littoral Côte d'Opale, Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV, UR 4492), 59140 Dunkerque, France 10.3762/bjoc.19.66 Keywords: building blocks; cyclodextrins; new materials; The continuous increase in the number of

• , and catalysis [2][5][12]. Molecular encapsulation is not the only application area for these macrocyclic components at present. CDs are versatile molecules. Their 3D structure makes them exceptional building blocks for the design of innovative supramolecular architectures due to the differential

Asymmetric tandem conjugate addition and reaction with carbocations on acylimidazole Michael acceptors

• Brigita Mudráková,
• Renata Marcia de Figueiredo,
• Jean-Marc Campagne and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 881–888, doi:10.3762/bjoc.19.65

• its applications in the total syntheses of complex natural products and other molecules of biological relevance [13][14]. Acylimidazoles proved to be versatile building blocks broadly applicable in asymmetric catalysis and organic synthesis. Today, acylimidazoles are used as ester/amide surrogates

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• struts and the photoresponsive linkers. The use of ditopic interlocked building blocks, such as that employed to form mainly a cyclic hetero[4]pseudorotaxane from a self-complementary [2]rotaxane [73], is also envisioned as a strategy that will be employed in the future to dynamically change the

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• (0)/PR3-catalyzed C3 or C4-arylation of nicotinic and isonicotinic acids using amide as a directing group (Scheme 27) [97]. This method provides a way for arylated nicotinic acid derivatives which serve as building blocks for biologically important molecules. This was the first report for a directing

Facile access to 3-sulfonylquinolines via Knoevenagel condensation/aza-Wittig reaction cascade involving ortho-azidobenzaldehydes and β-ketosulfonamides and sulfones

• Ksenia Malkova,
• Andrey Bubyrev,
• Stanislav Kalinin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2023, 19, 800–807, doi:10.3762/bjoc.19.60

• have developed a new convenient protocol for the synthesis of 3-sulfonyl-substituted quinolines (sulfonamides and sulfones). The approach is based on a Knoevenagel condensation/aza-Wittig reaction cascade involving o-azidobenzaldehydes and ketosulfonamides or ketosulfones as key building blocks. The

• synthesis of 3-sulfonyl-substituted quinolines (sulfonamides and sulfones). The approach is based on a Knoevenagel condensation/aza-Wittig reaction cascade for the quinoline core assembly. Hence, o-azidobenzaldehyde, ketosulfonamide or ketosulfone were utilized as key building blocks. The method devised

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• , sulfonamides and aryltrifluoroborates is described. This process provides modular access to the important α-arylglycine motif in moderate to good yields and enantioselectivies. The formed α-arylglycine products constitute useful building blocks for the synthesis of peptides or arylglycine-containing natural

• modular access to arylglycines from three readily available building blocks [10][11][12]. The Petasis borono-Mannich reaction usually proceeds in the absence of any external catalyst via zwitterionic intermediates and an intramolecular transfer of the aryl residue form the activated boronate to the

• decrease of the isolated yields. As already demonstrated in our previous work, the Pbf-protected arylglycine products can be directly used as building blocks for peptide synthesis [22]. Finally, we utilized our method for the preparation of a protected version of p-hydroxyphenylglycine (Scheme 5), a common

Synthesis of medium and large phostams, phostones, and phostines

• Jiaxi Xu

Beilstein J. Org. Chem. 2023, 19, 687–699, doi:10.3762/bjoc.19.50

• phosphorus-containing heterocyclic compounds [1][2] and significant agrochemicals [3], medicinal agents [4], and organic materials [5]. They are also organic synthetic intermediates and building blocks [6][7]. To date, only limited four-membered β-phostams [8][9], β-phostones and β-phostines [10] have been

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• Peter Kisszekelyi Radovan Sebesta Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia 10.3762/bjoc.19.44 Abstract Metal enolates are useful intermediates and building blocks indispensable in many

• building blocks providing an aminomethyl moiety upon adding nucleophiles. Protected formaldehyde aminals are useful synthetic equivalents to formaldehyde imines. The imine functionality can be unmasked (68) in the reaction medium by Lewis acids such as TiCl4. The formed Mg enolates 66 readily react with

• formylation products. The methodology was later exploited in the expedient synthesis of the Taxol core (Scheme 34) [71]. Tandem conjugate borylations and silylations Chiral organoboron compounds are well-known synthetic building blocks with diverse possibilities for subsequent derivatization (e.g., oxidation

C3-Alkylation of furfural derivatives by continuous flow homogeneous catalysis

• Grédy Kiala Kinkutu,
• Catherine Louis,
• Myriam Roy,
• Juliette Blanchard and
• Julie Oble

Beilstein J. Org. Chem. 2023, 19, 582–592, doi:10.3762/bjoc.19.43

• relevant building blocks on a large scale. Experimental Triphenylphosphine triruthenium undecacarbonyl (comp4) Following a slightly modified procedure compared to the one reported [41], triruthenium dodecacarbonyl (1.4 g, 2.19 mmol, 1 equiv) was dissolved in freshly distilled and degassed THF (0.036 M) at

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• were built using chiral amino acid building blocks and consequently have an intrinsic CD spectrum. While changes of poly rA–poly rU spectra upon titration with Phen-Py-1 and Phen-Py-2 were negligible (Figures S20 and S21, Supporting Information File 1), the addition of Phen-Py-1 and Phen-Py-2 to the ct

Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups

• Ita Hajdin,
• Romana Pajkert,
• Mira Keßler,
• Jianlin Han,
• Haibo Mei and
• Gerd-Volker Röschenthaler

Beilstein J. Org. Chem. 2023, 19, 541–549, doi:10.3762/bjoc.19.39

• ]. Therefore, as relevant building blocks, tremendous efforts have been made to develop reliable methods for their synthesis. Transition-metal-catalyzed cyclopropanation of alkenes with trifluoromethyldiazoalkanes is a commonly used synthetic strategy for the construction of trifluoromethylcyclopropanes

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• provide the reader a nice overview. Since reviews dealing with transition-metal-catalyzed functionalization of compounds by C–H bond activation with fluorinated reagents [60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77] and vinylic, allylic or propargylic fluorinated building blocks

Synthesis and reactivity of azole-based iodazinium salts

• Thomas J. Kuczmera,
• Annalena Dietz,
• Andreas Boelke and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 317–324, doi:10.3762/bjoc.19.27

• weak interactions with one of the triflates (I1–O3: 3.354 Å, I1–O5, 3.078 Å). We finally investigated the further reactivity of the synthesized azoiodazinium salts to elaborate their potential as synthetic building blocks (Scheme 1). Treatment of 5aa with Ac2O led to a non-selective ring opening at

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• iterative addition of geranyl (C10) or farnesyl (C15) building blocks derived from isoprene as starting unit and further structure rearrangement and functionalization [1]. This ubiquitous distribution highlights their pivotal role in living systems such as cell wall structural agent or ecological mediator

• articulated around a ring expansion of a fused cyclobutane/perhydroindanone fragment, leading to the cyclooctane motif. Interestingly, and unlike the previously reported strategies, the perhydroindanone precursor was prepared starting from achiral building blocks 157 and 158. They were engaged in a selective