Selective and scalable oxygenation of heteroatoms using the elements of nature: air, water, and light

• Damiano Diprima,
• Hannes Gemoets,
• Stefano Bonciolini and
• Koen Van Aken

Beilstein J. Org. Chem. 2023, 19, 1146–1154, doi:10.3762/bjoc.19.82

• phosphine oxide, and selenides to selenoxides. Sulfoxide, phosphine oxide, and selenoxide-containing molecules have diverse applications in the pharmaceutical industry [10], as chiral auxiliaries or as ligands for asymmetric metal catalysis [11], and in materials such as polymers [12][13] and flame

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

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• complex. Solubility of the t-Bu-containing ligand and its Schiff base complexes is increased, facilitating scaling-up the reaction procedure and isolation of the functionalized amino acid. Keywords: asymmetric synthesis; chiral auxiliaries; cysteine derivatives; Ni–Schiff base complexes; voltammetry

• employing chiral auxiliaries [4][5] and asymmetric phase-transfer catalysis [6][7]. The former approach is commonly based on the application of chiral derivatives of glycine containing structurally diverse chiral auxiliaries, both cyclic [8][9][10][11] and acyclic [12][13]. Transition-metal complexes

• )) and includes a chiral auxiliary, an amino acid, and a bifunctional linker capable to arrange the components in the Schiff base complex. Such templates provide a significant C–H acidity at the α-amino acid carbon and a possibility for recycling of the chiral auxiliaries (for reviews see [5][14][15][16

An efficient metal-free and catalyst-free C–S/C–O bond-formation strategy: synthesis of pyrazole-conjugated thioamides and amides

• Shubham Sharma,
• Dharmender Singh,
• Sunit Kumar,
• Vaishali,
• Rahul Jamra,
• Naveen Banyal,
• Deepika,
• Chandi C. Malakar and
• Virender Singh

Beilstein J. Org. Chem. 2023, 19, 231–244, doi:10.3762/bjoc.19.22

• ]. Substituted pyrazoles are also of considerable interest because of their synthetic utility as chiral auxiliaries [32], synthetic reagents in multicomponent reactions [33][34], and guanylating agents [35]. The installation of a thioamide functionality has attracted an immense attention in medicinal chemistry

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

• ]. Such scaffolds are widely utilized as versatile building blocks in the synthesis of biologically active compounds [3][4][5][6][7], chiral auxiliaries [8][9], and chiral ligands [10][11][12][13]. Traditional pinacol coupling reactions are performed with a stoichiometric or even excess amount of low

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

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

• -oxathiolane nucleosides via resolution methods. The chemical as well as enzymatic procedures are reviewed and segregated in this review for effective synthesis of 1,3-oxathiolane nucleoside analogues. Keywords: chiral auxiliaries; enzymes; Lewis acids; N-glycosylation; 1,3-oxathiolane sugar and nucleosides

• introduction on important classical approaches and older yet creative methods to provide the reader with a historical context. For comparison, this will be followed by a discussion of more modern techniques, including chiral auxiliaries for neighboring group participation and transition metal-catalyzed

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

• as an important synthetic strategy for the preparation of a large variety of β-amino carbonyl and similar motifs which are present in many bioactive natural products [8][9], antibiotics [10][11][12] and chiral auxiliaries [13][14][15]. However, the reaction of many nitrogen-nucleophiles, such as

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

• compounds and biaryl chiral auxiliaries. Also, the oxidative coupling of phenolic substrates has been reported to be mediated by vanadium complexes such as VCl4, VOCl3, and VOF3, among others. For instance, an intramolecular coupling of phenolic moieties using VOF3 has been reported as a final step in the

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

• imines derived from tert-butanesulfinamide. These imines are versatile chiral auxiliaries and have been extensively used as eletrophiles in a wide range of reactions. The electron-withdrawing sulfinyl group facilitates the nucleophilic addition of organometallic compounds to the iminic carbon with high

• ligands [52][53][54][55] and as chiral auxiliaries [56]. The most widely used synthetic methods to form the aziridine ring [57][58][59][60][61] include intramolecular cyclizations in amines bearing potential leaving groups. Stereoselective syntheses of aziridines have been successfully carried out by

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

• a trifluoromethylated iminium ion 187 during the course of their studies on a Strecker-type reaction [123]. Starting from trifluoromethylated imines 193 or oxazolidines 194 and 195 bearing enantiopure chiral auxiliaries, the authors accessed the corresponding cyano derivatives 196–198 with different

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• cyclopropane formation did not require Et3B (Scheme 25). The work was extended to include boron-free, diastereoselective versions incorporating N-acylimidazolidinone chiral auxiliaries (Scheme 26). Cyclization reaction of phenylacetonitrile and 1,2-dibromo-1,1-difluoroethane: Kagabu et al. showed that the

The biomimetic synthesis of balsaminone A and ellagic acid via oxidative dimerization

• Sharna-kay Daley and
• Nadale Downer-Riley

Beilstein J. Org. Chem. 2020, 16, 2026–2031, doi:10.3762/bjoc.16.169

• ; ellagic acid; oxidative dimerization; Introduction Over the last century, the formation of an aryl to aryl bond has garnered considerable synthetic attention due to the applications of biaryls as pharmaceutical agents, as well as chiral auxiliaries in asymmetric synthesis [1][2][3]. Methods such as the

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

• Esra Demir,
• Ozlem Sari,
• Yasin Çetinkaya,
• Ufuk Atmaca,
• Safiye Sağ Erdem and
• Murat Çelik

Beilstein J. Org. Chem. 2020, 16, 1805–1819, doi:10.3762/bjoc.16.148

• considerable use as antibiotics [1], immunomodulators [2], antibacterials [3], as well as synthetic intermediates and chiral auxiliaries for various organic conversions [4][5][6][7]. Linezolid [1][2][3] (3) and cytoxazone [8][9] (4) are oxazolidinone derivatives having significant biological activities

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• this area have established a number of asymmetric electrochemical inductors. After a thorough comprehension of the available literature, we propose to classify the chiral electrochemical inductors into three broad categories: chiral electrodes, chiral media and chiral auxiliaries [17]. We have

• 1994, Zielinski and Schäfer made a vital contribution in the field of asymmetric electrosynthesis in terms of the diastereoselective cathodic reduction of the carbonyl group of chiral phenylglyoxamides 150 and 152 [89][90]. After initial conversion to its corresponding amides using chiral auxiliaries

• phenylglyoxalic acid was further converted to mandelic acid derivatives 151 and 153, respectively, upon reduction at a mercury pool cathode. The electrolysis afforded an excellent chemical yield along with moderate to good diastereomeric excesses. Moreover, the recovery of chiral auxiliaries upon hydrolysis of

N-(1-Phenylethyl)aziridine-2-carboxylate esters in the synthesis of biologically relevant compounds

• Iwona E. Głowacka,
• Aleksandra Trocha,
• Andrzej E. Wróblewski and
• Dorota G. Piotrowska

Beilstein J. Org. Chem. 2019, 15, 1722–1757, doi:10.3762/bjoc.15.168

• of chemical and configurational stability was achieved by introducing N,N-dibenzylserinals 4 [10]. Another important strategy of asymmetric synthesis relies on chiral auxiliaries, i.e., a specially selected homochiral part of a starting material governing the stereoselectivity of subsequent reactions

Dirhodium(II)-catalyzed [3 + 2] cycloaddition of N-arylaminocyclopropane with alkyne derivatives

• Wentong Liu,
• Yi Kuang,
• Zhifan Wang,
• Jin Zhu and
• Yuanhua Wang

Beilstein J. Org. Chem. 2019, 15, 542–550, doi:10.3762/bjoc.15.48

• method has potential synthetic practicality by providing a convenient way to synthesize trans-cyclic β-amino acid derivatives. Further application of this method with other cycloaddition partners and asymmetric synthesis of the chiral ring with the help of chiral auxiliaries are currently underway

Synthesis of nonracemic hydroxyglutamic acids

• Dorota G. Piotrowska,
• Iwona E. Głowacka,
• Andrzej E. Wróblewski and
• Liwia Lubowiecka

Beilstein J. Org. Chem. 2019, 15, 236–255, doi:10.3762/bjoc.15.22

• ) also appeared attractive providing two or three predefined stereogenic centers. In more sophisticated approaches application of chiral auxiliaries allowed to generate vicinal or 1,3-aminoalcohol units of the required stereochemistries. Currently available synthetic methodologies towards hydroxyglutamic

Some mechanistic aspects regarding the Suzuki–Miyaura reaction between selected ortho-substituted phenylboronic acids and 3,4,5-tribromo-2,6-dimethylpyridine

• Piotr Pomarański,
• Piotr Roszkowski,
• Jan K. Maurin,
• Armand Budzianowski and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2018, 14, 2384–2393, doi:10.3762/bjoc.14.214

• ’-bromopyridinium N-(2’-pyrazinyl)aminides [17]. In 2014, a regiocontrolled polyarylation of pyridine was presented by Doebelin and co-workers [27]. Rotationally restricted biaryls are stereochemically and structurally important elements of a rapidly growing class of catalysts, natural products and chiral

• auxiliaries. Therefore, the atropselective synthesis is an important synthetic approach pursued by many research groups [22][23][24][25][26]. In 2015 the first phosphoric acid-catalysed asymmetric reactions of 2-naphthols with quinone analogues were described, allowing an access to a class of sterically

Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

• Fateh V. Singh,
• Priyanka B. Kole,
• Saeesh R. Mangaonkar and
• Samata E. Shetgaonkar

Beilstein J. Org. Chem. 2018, 14, 1778–1805, doi:10.3762/bjoc.14.152

• chiral auxiliaries 129a or 129b under similar reaction conditions mentioned in Scheme 48. Furthermore, the synthesized spiroketal 159 (R2 = iPr; R4 = SiMe3) was used as synthetic intermediate for enantioselective synthesis of natural product (−)-biscarvacrol [8] (Scheme 59). Additionally, Parra and

Diastereoselective auxiliary- and catalyst-controlled intramolecular aza-Michael reaction for the elaboration of enantioenriched 3-substituted isoindolinones. Application to the synthesis of a new pazinaclone analogue

• Romain Sallio,
• Stéphane Lebrun,
• Frédéric Capet,
• Francine Agbossou-Niedercorn,
• Christophe Michon and
• Eric Deniau

Beilstein J. Org. Chem. 2018, 14, 593–602, doi:10.3762/bjoc.14.46

• incorporate α-methylbenzylamine-type chiral auxiliaries, which have been extensively used by Davies et al. to gain access to a wide range of chiral N-heterocycles via intermolecular aza-Michael reactions [34][47][48][49][50][51]. The starting unsaturated benzoic acids 14a–e and 15 were readily prepared via a

• previously observed in other Michael-additions involving chiral auxiliaries on the nucleophile and on the Michael acceptor [62]. As for (S)-6a, catalyst 18c bearing a bulky tert-butyl group at the benzyl para-position gave the best results in term of stereoselectivity (80% de, Table 2, entry 7). However, the

Investigations towards the stereoselective organocatalyzed Michael addition of dimethyl malonate to a racemic nitroalkene: possible route to the 4-methylpregabalin core structure

• Denisa Vargová,
• Rastislav Baran and
• Radovan Šebesta

Beilstein J. Org. Chem. 2018, 14, 553–559, doi:10.3762/bjoc.14.42

• amino acids have also been investigated as treatments for ocular disorders [7]. However, the syntheses of this type of compounds were long and relied on the use of Evans chiral auxiliaries or chiral starting materials. Various GABA derivatives were synthesized using asymmetric organocatalysis

A mechanochemical approach to access the proline–proline diketopiperazine framework

• Nicolas Pétry,
• Hafid Benakki,
• Eric Clot,
• Pascal Retailleau,
• Farhate Guenoun,
• Fatima Asserar,
• Chakib Sekkat,
• Thomas-Xavier Métro,
• Jean Martinez and
• Frédéric Lamaty

Beilstein J. Org. Chem. 2017, 13, 2169–2178, doi:10.3762/bjoc.13.217

• chemists have used DKPs extensively as a synthetic platform, easily synthesized and stereochemically controlled, for the preparation of small bioactive molecules [4][5]. DKPs have also been considered as chiral auxiliaries in asymmetric synthesis [6]. Furthermore, the rigidity of the DKPs is a unique

Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces

• Loïc Pantaine,
• Vincent Humblot,
• Vincent Coeffard and
• Anne Vallée

Beilstein J. Org. Chem. 2017, 13, 648–658, doi:10.3762/bjoc.13.64

• applications in medicinal chemistry, sulfamide groups have been incorporated in self-assembling molecules [22][23][24][25][26][27], peptides [28], polymers [29], ligands [30], chiral auxiliaries [31][32][33] and in organocatalysts [34][35][36][37]. In light of the importance of the sulfamide functionality, our

Diastereoselective anodic hetero- and homo-coupling of menthol-, 8-methylmenthol- and 8-phenylmenthol-2-alkylmalonates

• Matthias C. Letzel,
• Hans J. Schäfer and
• Roland Fröhlich

Beilstein J. Org. Chem. 2017, 13, 33–42, doi:10.3762/bjoc.13.5

• Matthias C. Letzel Hans J. Schafer Roland Frohlich Organisch-Chemisches Institut der Westfälischen Wilhelms- Universität, Corrensstraße 40, D-48149 Münster, Germany 10.3762/bjoc.13.5 Abstract Diastereoselective radical coupling was achieved with chiral auxiliaries. The radicals were generated by

• reason, we were interested in exploring the structural influence of chiral auxiliaries (Figure 1) and the carboxylic acid on the diastereoselectivity in the anodic coupling of carboxylic acids. We report here on the diastereoselectivity found in the anodic hetero- and homo-coupling of menthol- (1)-, 8

• so far successful reagents LiAlH4 and DIBAL. Therefore, in the future bulky chiral auxiliaries must be developed that can be partially disassembled before their cleavage and slim cleavage reagents have to be found and explored. Conclusion We developed an efficient procedure for the synthesis of