Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• (+)-lasiol was achieved through a highly selective SN2 substitution (SN2/SN2' = >99:1, dr = 98:2, 99% ee), while the preparation of (+)-13-norfaranal and (+)-faranal showcased the versatility of the methodology in constructing more complex terpene frameworks. These successful applications in natural product

• synthesis underscore the robustness and reliability of this copper-mediated transformation in creating stereochemically complex molecules. Mechanistic investigations revealed several key factors controlling the stereochemical outcome of these transformations. The extremely low temperature (−100 °C) during

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• multi-substituted benzo[j]fluoranthene derivatives, which have the potential to be useful in natural product synthesis. However, all oxygens in compound 18 are protected as methyl ethers, and therefore, demethylating one or some of these methoxy groups selectively is anticipated to be extremely

Visible-light-mediated flow protocol for Achmatowicz rearrangement

• Joachyutharayalu Oja,
• Sanjeev Kumar and
• Srihari Pabbaraja

Beilstein J. Org. Chem. 2024, 20, 2493–2499, doi:10.3762/bjoc.20.213

• product synthesis. Scope of the integrated continuous photo-flow (visible light)-induced Achmatowicz rearrangement reaction. Reaction conditions: Stock solution (A) comprise of 2/K2S2O8/Ru(bpy)3Cl·6H2O/ACN/DMSO/H2O in a molar ratio of 1:1:0.005:70:54:408; yields are based on isolated yields. Proposed

• as sun light, as a greener approach and easily available biomass-derived furfuryl alcohols as starting materials. The flow platform with the developed protocol was utilized successfully to make several dihyropyranones that may find wide applications in medicinal and materials chemistry and natural

Methyltransferases from RiPP pathways: shaping the landscape of natural product chemistry

• Maria-Paula Schröder,
• Isabel P.-M. Pfeiffer and
• Silja Mordhorst

Beilstein J. Org. Chem. 2024, 20, 1652–1670, doi:10.3762/bjoc.20.147

• byproduct. This observation suggests a novel mechanism for indole C4 methylation by NosN [131][134]. S-Methyltransferases S-MTs are rare in RiPP biosynthesis and in natural product synthesis in general. There are few examples, and in most cases, the characterisation of the MT does not go beyond deletion

Oxidative hydrolysis of aliphatic bromoalkenes: scope study and reactivity insights

• Amol P. Jadhav and
• Claude Y. Legault

Beilstein J. Org. Chem. 2024, 20, 1286–1291, doi:10.3762/bjoc.20.111

• heterocyclic compounds [20][21][22]. Particularly dialkyl bromoketones have been utilized in natural product synthesis [23][24][25], also as a precursor to reactive oxyallyl cation intermediates [26][27][28], and for their photochemical reactions [29]. However, the direct halogenation of unsymmetrical ketones

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• . This methodology has been applied to diverse areas of chemistry, including natural product synthesis [45][46], medicinal chemistry [47][48], polymer chemistry [49][50] and porphyrin chemistry [51][52][53]. In recent years, green chemistry has become a widely used method for organic synthesis in order

Total synthesis: an enabling science

• Bastien Nay

Beilstein J. Org. Chem. 2023, 19, 474–476, doi:10.3762/bjoc.19.36

• synthetic methodology developments and to natural product isolation or biosynthesis. Thus, thematic issues dealing with total synthesis in the Beilstein Journal of Organic Chemistry have naturally been published in these fields, such as "Transition-metal and organocatalysis in natural product synthesis

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

• found multiple applications in natural product synthesis [65]. Employed in C–C bond-formation reactions, this single-electron reducing agent has been particularly useful for five- to eight-membered ring cyclizations [65]. Its tunable reactivity opens access to both radical and anionic processes, hence

• favoring reactivity with various types of substrates, ranging from halides to carbonyls and alkenes/alkynes. It is comprehensible that this reagent attracted early interest in natural product synthesis and more precisely on medium-sized ring formation. 4.1 SmI2-mediated Barbier-type ring annulation towards

Sequential hydrozirconation/Pd-catalyzed cross coupling of acyl chlorides towards conjugated (2E,4E)-dienones

• Benedikt Kolb,
• Daniela Silva dos Santos,
• Sanja Krause,
• Anna Zens and
• Sabine Laschat

Beilstein J. Org. Chem. 2023, 19, 176–185, doi:10.3762/bjoc.19.17

• Benedikt Kolb Daniela Silva dos Santos Sanja Krause Anna Zens Sabine Laschat Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany 10.3762/bjoc.19.17 Abstract Dienones are challenging building blocks in natural product synthesis due to their high

• , which might be incompatible with existing functional groups and/or the stereochemical integrity [18][22]. Especially in natural product synthesis, dienone functional groups suffer from isomerization and polymerization [23]. Therefore, a late stage introduction of dienone units is advantageous [24

• through this approach. As the sequential hydrozirconation/Pd-catalyzed acylation worked reasonably well for aliphatic substrates, we surmised that terpene-derived enynes might be suitable starting materials for natural product synthesis. For this purpose, two terpene enynes 25p and 25q were synthesized

Modern flow chemistry – prospect and advantage

• Philipp Heretsch

Beilstein J. Org. Chem. 2023, 19, 33–35, doi:10.3762/bjoc.19.3

• natural product synthesis programs [3], has revealed some inadequacies, particularly in view of the equipment and procedures available. These limitations have been slowly overcome with many creative but sometimes highly “academic” solutions. Thus, recent years witnessed a steady increase in the

• typically call for an optimized or even specifically designed reactor built, the modularity of flow reactor is vital for quick reconfiguration and switching between different reactions. This argument is particularly true when natural product synthesis is to be performed in continuous flow. The need for

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• ” [8]. And this is where divergent total synthesis might help. Divergent total synthesis is an old but yet underdeveloped strategy, utilizing the conceptual advantages of biosynthetic routes that allow multi-target natural product synthesis through a unified synthetic plan [9][10]. Based on the logic

• -mediated photocatalysis (using Pd(PPh3)2Cl2 in combination with xantphos) [112] towards 244, followed by Mukaiyama hydration with the aid of Mn(dpm)3, dioxygen, and PhSiH3 for the synthesis of kadsuphilin N (234). Conclusion The utility of radical retrosynthetic disconnections in natural product synthesis

On drug discovery against infectious diseases and academic medicinal chemistry contributions

• Yves L. Janin

Beilstein J. Org. Chem. 2022, 18, 1355–1378, doi:10.3762/bjoc.18.141

• in part due to their usefulness in medicinal chemistry [278] and research to reach even more elaborated amines is warranted. Concerning natural product synthesis, which has been the main source of chemical synthesis challenges in the last century, Paul Wender’s approach consisting in also reaching

Vicinal ketoesters – key intermediates in the total synthesis of natural products

• Marc Paul Beller and
• Ulrich Koert

Beilstein J. Org. Chem. 2022, 18, 1236–1248, doi:10.3762/bjoc.18.129

• reagents. The presented examples may encourage the use of vicinal ketoesters in future applications, in particular in the field of natural product synthesis. Structures of vicinal ketoesters and examples for their typical reactivity. Doyle’s diastereoselective intramolecular aldol addition of α,β

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

• natural product synthesis, pigments and dyes. Different variety of α-amino carbonyls [2], α-amino acids [3] and 1,2-diamines were prepared from the nitriles using homogeneous and heterogeneous catalysis [4][5][6]. One of the astonishing aspects of nitriles is that it can be easily converted to amines

Synthesis of 1-indolyl-3,5,8-substituted γ-carbolines: one-pot solvent-free protocol and biological evaluation

• Premansh Dudhe,
• Mena Asha Krishnan,
• Kratika Yadav,
• Diptendu Roy,
• Krishnan Venkatasubbaiah,
• Biswarup Pathak and
• Venkatesh Chelvam

Beilstein J. Org. Chem. 2021, 17, 1453–1463, doi:10.3762/bjoc.17.101

• purification reduce the efforts in the synthesis of complex molecular architectures. Therefore, cascade reactions are essential in synthetic organic chemistry, even with moderate yields [26]. Recently, such reactions have claimed their much deserving place in drug design and natural product synthesis [27]. In

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

• , and pharmaceutical agents. These structural motifs are frequently used as synthons and as key intermediates for natural product synthesis. Therefore, the development of stereoselective synthetic methods for the substituted THP subunit has long been the area of fundamental research in organic chemistry

• information showcases the knowledge gained in this area. In either case, it is hoped that the challenge of stereoselective construction of THP rings in the context of natural product synthesis will continue to inspire synthetic chemists to develop new methods in the coming years. General strategy for the

All-carbon [3 + 2] cycloaddition in natural product synthesis

• Zhuo Wang and
• Junyang Liu

Beilstein J. Org. Chem. 2020, 16, 3015–3031, doi:10.3762/bjoc.16.251

• -carbon quaternary centers in a single step and has been demonstrated in the synthesis of complex natural products. In this review, we present the development of all-carbon [3 + 2] cycloadditions and illustrate their application in natural product synthesis reported in the last decade covering 2011–2020

• (inclusive). Keywords: all-carbon; cyclization; [3 + 2] cycloaddition; natural product synthesis; stereocenters; Introduction The highly-substituted, stereo-congested, five-membered carbocycle containing contiguous stereocenters is one of the most common structural features in many structurally complicated

• as the phosphine-catalyzed [3 + 2] cycloaddition [17], platinum-catalyzed [3 + 2] cycloaddition [18], and Rhodium-catalyzed [3 + 2] cycloaddition [12], were invented and have been extensively used in natural product synthesis in the last decade. Many reviews focusing the method development of the all

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates

• Olusesan K. Koleoso,
• Matthew Turner,
• Felix Plasser and
• Marc C. Kimber

Beilstein J. Org. Chem. 2020, 16, 1983–1990, doi:10.3762/bjoc.16.165

• innovative transformations, including cycloadditions [5][6][7][8][9], intramolecular cyclizations and intermolecular addition reactions [10][11][12][13][14][15][16][17][18], as well as the use of the allenamide building block in natural product synthesis [1]. Addition reactions of allenamides, which can also

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• for modern synthetic chemistry, and we believe that the application in natural product synthesis and meta functionalization is highly desirable. In addition to this, to provide high selectivities and to allow for the combination of dual photoredox catalysis with HAT, the discovery of more effective

Formation of alkyne-bridged ferrocenophanes using ring-closing alkyne metathesis on 1,1’-diacetylenic ferrocenes

• Celine Bittner,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2019, 15, 2534–2543, doi:10.3762/bjoc.15.246

• alkyne metatheses. A selection of such complexes is shown in Figure 1. Molybdenum alkylidyne complex I with siloxide ligands (X = OSiPh3) [10][11] is widely used in natural product synthesis, predominantly through ring-closing alkyne metathesis (RCAM) [12][13][14][15][16][17][18][19][20]. The metathesis

An overview of the cycloaddition chemistry of fulvenes and emerging applications

• Ellen Swan,
• Kirsten Platts and
• Anton Blencowe

Beilstein J. Org. Chem. 2019, 15, 2113–2132, doi:10.3762/bjoc.15.209

• synthetically interesting scaffolds have been synthesised, including products which exhibit biological activity, complex ligands in coordination chemistry, and several natural product skeletons (Table 3). Applications of fulvene cycloadditions Organic and natural product synthesis A variety of organic molecules

• al. developed a programmable enantioselective one-pot synthesis of molecules with eight stereocentres greatly improving the efficiency of natural product synthesis [83]. Each of these natural products are biologically active, hence their total synthesis will allow further characterisation of their

• fuelled advances in organic and natural product synthesis, dynamic combinatorial chemistry and materials science, including dynamers, hydrogels and charge transfer complexes. The recent advances show that potential applications for fulvene cycloaddition reactions are varied and wide in scope. We believe

Robust perfluorophenylboronic acid-catalyzed stereoselective synthesis of 2,3-unsaturated O-, C-, N- and S-linked glycosides

• Madhu Babu Tatina,
• Xia Mengxin,
• Rao Peilin and
• Zaher M. A. Judeh

Beilstein J. Org. Chem. 2019, 15, 1275–1280, doi:10.3762/bjoc.15.125

• blocks especially for natural product synthesis [36][37][38][39][40]. Therefore, we used the perfluorophenyl boronic acid catalyst in the reaction between 2,3,4,6-tetra-O-acetyl-D-glucal (1a) and benzyl alcohol, n-butyl alcohol, cyclohexyl alcohol and p-toluenethiol (Figure 2). Gratifyingly, the reaction

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

• Yue Zhong,
• Wen-Yu Wu,
• Shao-Peng Yu,
• Tian-Yuan Fan,
• Hai-Tao Yu,
• Nian-Guang Li,
• Zhi-Hao Shi,
• Yu-Ping Tang and
• Jin-Ao Duan

Beilstein J. Org. Chem. 2019, 15, 291–298, doi:10.3762/bjoc.15.26

• reactivity, shorter reaction times, and higher yields of the target compounds. Meanwhile, these flexible approaches to the phenanthrene derivatives would be expected to provide significant references to material chemistry, pharmaceutical agents and natural product synthesis. Experimental General remarks All

Stereodivergent approach in the protected glycal synthesis of L-vancosamine, L-saccharosamine, L-daunosamine and L-ristosamine involving a ring-closing metathesis step

• Pierre-Antoine Nocquet,
• Aurélie Macé,
• Frédéric Legros,
• Jacques Lebreton,
• Gilles Dujardin,
• Sylvain Collet,
• Arnaud Martel,
• Bertrand Carboni and
• François Carreaux

Beilstein J. Org. Chem. 2018, 14, 2949–2955, doi:10.3762/bjoc.14.274

• glycal scaffolds are versatile building blocks with multiple applications in the field of natural product synthesis [6], the development of new asymmetric synthetic sequences with stereochemical diversity is still of high interest. Different approaches have been reported for the asymmetric synthesis of

The mechanochemical synthesis of quinazolin-4(3H)-ones by controlling the reactivity of IBX

• Md Toufique Alam,
• Saikat Maiti and
• Prasenjit Mal

Beilstein J. Org. Chem. 2018, 14, 2396–2403, doi:10.3762/bjoc.14.216

• highlights the advancement of quinazolin-4(3H)-ones synthesis chemistry and may find application in the context of mechanochemical reactions towards natural product synthesis and pharmaceutical chemistry. Experimental General methods. Ball-milling experiments were carried out open to atmosphere and at room