Unexpected chiral vicinal tetrasubstituted diamines via borylcopper-mediated homocoupling of isatin imines

• Marco Manenti,
• Leonardo Lo Presti,
• Giorgio Molteni and
• Alessandra Silvani

Beilstein J. Org. Chem. 2022, 18, 303–308, doi:10.3762/bjoc.18.34

• Marco Manenti Leonardo Lo Presti Giorgio Molteni Alessandra Silvani Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, Milano, 20133, Italy 10.3762/bjoc.18.34 Abstract Addressing the asymmetric synthesis of oxindole-based α-aminoboronic acids, instead of the expected

• oxindole-based α-aminoboronates. The asymmetric synthesis of diverse α-aminoboronic acids by diastereoselective Cu(I)-catalyzed borylation of N-tert-butanesulfinyl aldimines was described by Ellman and co-workers for the first time in 2008 [15] and next further developed with a more stable Cu(II) catalyst

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• only for pharmaceutical and fine chemical industries, but also for fragrance, flavor, agrochemical, and food industries [4]. Consequently, the importance of axially chiral compounds has been widely recognized in both academic and industrial chemical societies [5]. Therefore, asymmetric synthesis of

• phosphoric acid-catalyzed synthesis of axially chiral compounds and to suggest that much more attention should be paid to these catalysts in order to promote asymmetric synthesis. Review 1. Enantioselective synthesis of atropisomeric biaryls Direct C–H functionalization strategies for the atroposelective

• poor chemoselectivity [40]. However, the realization of this redox-neutral aryl–aryl cross-coupling is a formidable challenge. Therefore, the discovery of efficient catalysts and ligands to achieve high stereoselectivity is a fundamental issue in catalytic asymmetric synthesis [14]. In this section, we

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

• to treat HIV infection [58] as well as human chronic hepatitis B [59]. Using asymmetric synthesis or resolution with appropriate enzymes to prepare these enantiopure 1,3-oxathiolanes has gained extensive attention due to the good stereoselectivity, high efficiency, mild reaction conditions, and eco

• nuclear Overhauser effect (NOE) NMR spectroscopy are useful tools to monitor and control the chirality when utilizing a modified 1,3-oxathiolane intermediate 65 obtained via enzyme-catalyzed selective hydrolysis. Hu et al. [61] established a green catalyst, STS, for the asymmetric synthesis of lamivudine

• nucleoside 1a in a protocol by Vorbrüggen et al. In turn, using STS, this valuable asymmetric synthesis provided the intermediate 65, which led to lamivudine (1). Recently, Chen at al. [62] reported the isolation of the strain Klebsiella oxytoca from soil by a target-oriented process, and it was utilized as

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

• . Asymmetric synthesis of chiral N-functionalized heteroarenes. Asymmetric cascade aza-Michael−aldol reactions of α,β-unsaturated ketones with pyrroles. Intramolecular aza-Michael addition of conjugated ketones. Intramolecular enantioselective aza-Michael addition. Asymmetric aza-Michael addition of 4

• -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

• features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis

• , tandem reactions, and the total synthesis and biosynthesis of natural products. This review explores the use of α-ketol rearrangements in these contexts over the past two decades. Keywords: acyloin rearrangement; asymmetric synthesis; iminol rearrangement; ketol rearrangement; tandem reactions

• reactions through mid-2002 have been thoroughly discussed in a past review by Paquette [1]. The current review expands on that work by providing an updated account from mid-2002 through early 2021, including the following recently developed applications: asymmetric synthesis, total synthesis, tandem

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• Najeh Tka Mohamed Adnene Hadj Ayed Mourad Ben Braiek Mahjoub Jabli Peter Langer Laboratory of Asymmetric Synthesis and Molecular Engineering for Organic Electronic Materials (LR18ES19), Monastir University, Faculty of Sciences of Monastir, Environment street, 5019 Monastir, Tunisia Universität

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

• corresponding bicyclic dihydropyrans 119 and 121, respectively (Scheme 36). Later, Namba et al. reported the synthesis of racemic vinylindoline derivatives 123 from N-tosylanilinoallylic alcohol derivative 122 by using 1–2 mol % of Hg(OTf)2 in CH2Cl2 at room temperature [90]. An asymmetric synthesis of

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

• examples, and the advance of anion-binding-catalyzed strategies involving more complex H-bonding networks clearly highlight that it is indeed possible to mimic enzyme-like structures with small-molecule catalysts for asymmetric synthesis. Conclusion In the past two decades, tremendous advances in the field

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

• , the advances in asymmetric organocatalyzed synthesis of coumarin derivatives are discussed in this review, according to the mode of activation of the catalyst. Keywords: asymmetric synthesis; green chemistry; 2H-chromen-2-one; organocatalysis; Introduction Coumarins are important naturally occurring

• ammonium salts derived from cinchona alkaloids [28]. Therefore, the asymmetric synthesis of coumarin derivatives is herein presented according to the activation mode, i.e., via covalent or non-covalent bonding. Furthermore, the use of bifunctional catalysts and multicatalysis are discussed as well

• product 17 was obtained in 15 steps with 6% overall yield. Although chiral secondary amines have proved to be particularly useful catalysts, primary amines as organocatalysts in asymmetric synthesis have also played a significant role [36]. For instance, Kim et al. described the enantioselective Michael

2,4-Bis(arylethynyl)-9-chloro-5,6,7,8-tetrahydroacridines: synthesis and photophysical properties

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli,
• Noureddine Chaaben,
• Kamel Alimi,
• Stefan Jopp and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 1629–1640, doi:10.3762/bjoc.17.115

• Najeh Tka Mohamed Adnene Hadj Ayed Mourad Ben Braiek Mahjoub Jabli Noureddine Chaaben Kamel Alimi Stefan Jopp Peter Langer Asymmetric Synthesis and Molecular Engineering Laboratory for Organic Electronic Materials, Faculty of sciences of Monastir, Monastir university, Environment street, 5019

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

• heterocycles. The present work will comprehensively cover the most pertinent contributions to this research area from 2012 to 2020. We regret in advance that some contributions are excluded in order to maintain a concise format. Keywords: asymmetric synthesis; chiral auxiliary; natural products; nitrogen

• important tool in the asymmetric synthesis of aziridines [25][26], α-amino acids [27][28], β-amino acids [23][29] and branched α-amines [30][31]. The Darzens-type asymmetric synthesis of N-(p-toluenesulfinyl)aziridine 2-carboxylate esters (7 and 8) was described through the addition of lithium α

• -butanesulfonamide and applications in some nucleophilic additions, the next sections will describe the synthesis of several alkaloids according to the size of the heterocycles. We regret in advance that some contributions are excluded in order to maintain a concise format. Review Asymmetric synthesis of aziridines

Prins cyclization-mediated stereoselective synthesis of tetrahydropyrans and dihydropyrans: an inspection of twenty years

• Asha Budakoti,
• Pradip Kumar Mondal,
• Prachi Verma and
• Jagadish Khamrai

Beilstein J. Org. Chem. 2021, 17, 932–963, doi:10.3762/bjoc.17.77

• , followed by removal of trimethylsilane (Scheme 50). The authors further explored this strategy for the asymmetric synthesis of 3-vinylidene-substituted tetrahydropyran by taking the chiral propargylsilane. A diastereoselective route to cis-2,6-disubstituted tetrahydropyran-4-one 215 was explored by

Chiral isothiourea-catalyzed kinetic resolution of 4-hydroxy[2.2]paracyclophane

• David Weinzierl and
• Mario Waser

Beilstein J. Org. Chem. 2021, 17, 800–804, doi:10.3762/bjoc.17.68

• polymer chemistry [1][2][7][8][9], these planar chiral molecules have been very successfully used in asymmetric catalysis [3][4][10][11][12]. Accordingly, the development of methods for the asymmetric synthesis of enantiomerically pure, or at least enantiomerically enriched, derivatives that can be

• decades, it was shown that enantioenriched 2 may serve as a valuable building block to access more advanced chiral cyclophane ligands and catalysts [3][4][19][20][21][22] and therefore its asymmetric synthesis became an important task [3][4][18][19][20][21][22][23][24][25][26][27]. Several strategies to

The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

• Deniz Tözendemir and
• Cihangir Tanyeli

Beilstein J. Org. Chem. 2021, 17, 494–503, doi:10.3762/bjoc.17.43

• %) catalyst loading. Selected enantiomerically enriched sulfa-Michael addition products were subjected to oxidation to obtain the corresponding sulfones. Keywords: asymmetric synthesis; bifunctional catalysis; cinchona alkaloids; organocatalysis; sulfa-Michael reaction; Introduction Derivatives of the

Synthetic strategies of phosphonodepsipeptides

• Jiaxi Xu

Beilstein J. Org. Chem. 2021, 17, 461–484, doi:10.3762/bjoc.17.41

• the P–C bond of the spirophosphoranes 201 readily proceeded at room temperature in the presence of moist solvents to give the corresponding phosphonodepsipeptides 202 in high yields (Scheme 37) [56]. An asymmetric synthesis of this class of phosphonodepsipeptides was realized with enantiopure (S)-α

• -hydroxyisovaleric acid-derived spirophosphoranes as the phosphorus reagents [57]. By using a similar strategy, linker-linked bisphosphonodepsidipeptides were synthesized [10]. The current method is also an interesting synthetic strategy of phosphonodepsipeptides. It can realize an asymmetric synthesis of

Direct synthesis of anomeric tetrazolyl iminosugars from sugar-derived lactams

• Michał M. Więcław and
• Bartłomiej Furman

Beilstein J. Org. Chem. 2021, 17, 115–123, doi:10.3762/bjoc.17.12

• Michal M. Wieclaw Bartlomiej Furman Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland 10.3762/bjoc.17.12 Abstract Herein we present the direct asymmetric synthesis of tetrazole-functionalized 1-deoxynojirimycin derivatives from simple sugars via a

Recent progress in the synthesis of homotropane alkaloids adaline, euphococcinine and N-methyleuphococcinine

• Dimas J. P. Lima,
• Antonio E. G. Santana,
• Michael A. Birkett and
• Ricardo S. Porto

Beilstein J. Org. Chem. 2021, 17, 28–41, doi:10.3762/bjoc.17.4

• subjected to simultaneous catalytic hydrogenation and hydrogenolysis of the protecting group Cbz to give (−)-adaline (1) in 90% yield. The asymmetric synthesis achieved by Liebeskind et al. presented a high enantiomeric excess and good yields. Also, the proposed route differed from the previously mentioned

Convenient access to pyrrolidin-3-ylphosphonic acids and tetrahydro-2H-pyran-3-ylphosphonates with multiple contiguous stereocenters from nonracemic adducts of a Ni(II)-catalyzed Michael reaction

• Alexander N. Reznikov,
• Dmitry S. Nikerov,
• Anastasiya E. Sibiryakova,
• Victor B. Rybakov,
• Evgeniy V. Golovin and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2020, 16, 2073–2079, doi:10.3762/bjoc.16.174

• analogues 4 and 5 are neuraminidase inhibitors (Figure 1) [8][9]. These circumstances create an interest in discovering synthetic routes for obtaining nonracemic phosphoryl-substituted heterocycles. Thus, in recent years, effective methods for the asymmetric synthesis of chiral phosphonates containing

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

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• asymmetric synthesis of a (Z)-2-hydroxy-3-pentene unit, with most proceeding via the cis-reduction of 4-acetoxy-2-pentynoic acid (13). The synthesis by Kitahara et al. [8][9] is the exception, where the chiral center is derived from relatively inexpensive (S)-ethyl lactate (14). This was transformed into the

Stereoselective Biginelli-like reaction catalyzed by a chiral phosphoric acid bearing two hydroxy groups

• Xiaoyun Hu,
• Jianxin Guo,
• Cui Wang,
• Rui Zhang and
• Victor Borovkov

Beilstein J. Org. Chem. 2020, 16, 1875–1880, doi:10.3762/bjoc.16.155

• activities [7][8]. For example, (S)-monastrol is 15-fold more effective in the inhibition of Eg 5 ATPase than its enantiomer, (R)-monastrol [9]. As more reports on the enantiospecific biological activity of DMPMs came to light, the development of an efficient and reliable asymmetric synthesis of enantiopure

On the hydrolysis of diethyl 2-(perfluorophenyl)malonate

• Ilya V. Taydakov and
• Mikhail A. Kiskin

Beilstein J. Org. Chem. 2020, 16, 1863–1868, doi:10.3762/bjoc.16.153

• ., pharmacologically active substances [1][2][3][4][5], in asymmetric synthesis and catalysis [6][7][8], as precursors of heterocyclic compounds [9][10][11], as ligands in coordination chemistry [12][13][14][15][16] and for other applications [17][18]. Incorporation of fluorine atoms into an organic molecule is known

Pauson–Khand reaction of fluorinated compounds

• Jorge Escorihuela,
• Daniel M. Sedgwick,
• Alberto Llobat,
• Mercedes Medio-Simón,
• Pablo Barrio and
• Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

• fluorine-containing N-tethered 1,7-enynes [61]. Intramolecular PKR of chiral N-tethered fluorinated 1,7-enynes [61]. Examples of further modifications to the Pauson−Khand adducts [61]. Asymmetric synthesis the fluorinated enynes 53. Intramolecular PKR of chiral N-tethered 1,7-enynes 53 [64]. Intramolecular

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• performed the absolute asymmetric synthesis of highly rigid thietane-fused β-lactams 356 from achiral monothioimides 355 using a chiral crystal environment through a topochemically controlled intramolecular photochemical [2 + 2] cycloaddition in a benzene solution. Only the 2-methylacrylamide derivative

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

• Svetlana A. Kuznetsova,
• Alexander S. Gak,
• Yulia V. Nelyubina,
• Vladimir A. Larionov,
• Han Li,
• Michael North,
• Vladimir P. Zhereb,
• Alexander F. Smol'yakov,
• Artem O. Dmitrienko,
• Michael G. Medvedev,
• Igor S. Gerasimov,
• Ashot S. Saghyan and
• Yuri N. Belokon

Beilstein J. Org. Chem. 2020, 16, 1124–1134, doi:10.3762/bjoc.16.99

• ][31], gas separation and absorption [28][29], enzyme encapsulation [36], and even asymmetric synthesis (albeit with a framework that contained a transition metal ion) [37]. However, for the HOF and CAHOF catalysts to have a similar appeal to other regular active site distribution materials, such as