Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• developments and illustrates the influences of copper salt, ligand, and substitution pattern of the substrate on the regioselectivity and stereoselectivity. Keywords: copper-catalysis; copper vinyl allenylidene intermediate; 1,3-enyne; 1,4-enyne; yne-allylic substitution; Introduction Copper is earth

• -abundant, inexpensive, relatively stable, and low toxic. Copper-catalyzed asymmetric allylic [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] and propargylic [23][24][25][26][27][28][29][30][31][32] substitutions are effective strategies for constructing new C–C and C

Metal-catalyzed coupling/carbonylative cyclizations for accessing dibenzodiazepinones: an expedient route to clozapine and other drugs

• Amina Moutayakine and
• Anthony J. Burke

Beilstein J. Org. Chem. 2024, 20, 193–204, doi:10.3762/bjoc.20.19

• was via the Chan–Lam amination (milder conditions, cheaper, earth-abundant catalyst, no expensive ligand requirement) as the Buchwald–Hartwig amination required harsher conditions and an expensive metal catalyst, and also gave an unwanted phenazine side product. The sequential stepwise Chan–Lam

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• its physicochemical properties. Moreover, we tailored a fully earth-abundant photocatalytic system to achieve specifically CO2 reduction, optimizing efficiency and selectivity. By changing the conditions, we enhanced the turnover number (TON) of CO production from only 0.5 to more than 60 and the

• ) complex; earth-abundant; hexafluoropropanol; photocatalytic CO2 reduction; Introduction Solar energy conversion into chemical energy addresses the issues of energy shortage with the exploitation of renewable sources [1]. Photoinduced CO2 reduction is included in the vast research field of artificial

• major components, fostering or dropping the efficiency. Thus, a rational design of novel molecular catalysts should consider an additional development of the whole system [7]. Moreover, it would be beneficial for future applications, if major efforts are focused on earth-abundant materials [8][9][10][11

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• driven by several key features of RLT catalysis, including the ability to form diverse bonds (including C–X, C–N, and C–S), the use of simple earth abundant element catalysts, and the intrinsic compatibility of this approach with varied radical generation methods, including HAT, radical addition, and

• decarboxylation. Here, we provide an overview of the evolution of RLT catalysis from initial studies to recent advances and provide a conceptual framework we hope will inspire and enable future work using this versatile elementary step. Keywords: catalysis; cooperative catalysis; earth abundant elements

• the power of RLT to install a variety of medicinally relevant groups, largely mirroring the selectivity of CYP450s. Intriguingly, studies by Groves have revealed earth abundant iron and manganese to be particularly privileged for this application of RLT, a major advantage for sustainable method

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• sacrificial donors [40]. More recently, other groups have published the electrochemical hydrogenation of carbonyl compounds using more earth-abundant electrocatalysts. For instance, Siewert and co-worker used a manganese complex as an electrocatalyst for the chemoselective carbonyl hydrogenation [41

• predominantly earth-abundant materials. The recycling of NADH analogues has been carried out using precious metal complexes, such as [CpRh(bpy)(H2O)]2+ [47]. This rhodium complex was adhered to a photoelectrode in a photoelectrochemical cell which also contained a second photoelectrode functionalized with a set

• -imidazolate itself as a donor. However, regenerated donors would need to be stored in large amounts to fuel a carbon dioxide reduction process at an industrially relevant rate. This means that they would have to be inexpensive, easy to synthesize, and made from earth abundant materials. They would also have

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

• -tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene))) as the first example of an earth-abundant transition metal complex capable of accumulating two photon energies via consecutive 2LMCT and 3MLCT excitations in an overall conPET mechanism [94]. Since iron-based photocatalysts generally suffer notoriously short

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• sketched in red, with newly formed cyclic structures being highlighted. Review Earth-abundant metals Among the transition metal used in organic synthesis, the late transition metals like rhodium, palladium, and iridium have taken center stage when it comes to methodology development. Although these late

• -stage transition metals have contributed immensely to synthetic organic and organometallic chemistry, increasing societal awareness in terms of sustainable developments and resource management has prompted chemists to explore the use of environmentally benign, inexpensive, and earth-abundant metals [18

• active Cu(I) catalyst. The reaction was broadly successful with the steric and electronic nature of the aryl iodide having little effect on the reaction. Iron-catalyzed reactions Being the most earth-abundant d-block element, as well as orders of magnitude less expensive than other transition-metal

B–N/B–H Transborylation: borane-catalysed nitrile hydroboration

• Filip Meger,
• Alexander C. W. Kwok,
• Franziska Gilch,
• Dominic R. Willcox,
• Alex J. Hendy,
• Kieran Nicholson,
• Andrew D. Bage,
• Thomas Langer,
• Thomas A. Hunt and
• Stephen P. Thomas

Beilstein J. Org. Chem. 2022, 18, 1332–1337, doi:10.3762/bjoc.18.138

• research into the development of new catalytic methodologies, specifically those that use Earth-abundant and low toxicity elements, as an alternative to transition-metal catalysis [9][10]. Using metal-free catalytic systems, including boron-based catalysts, circumvents some of the issues associated with

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• nature. Furthermore, the 3d transition metals show contrast in the reactive nature with 4d and 5d group members [19]. Catalysts based on Earth abundant metals such as Fe and Co are promising members of the 3d series in catalysis [20]. Recently, catalysts based on iron and cobalt complexes have been

Earth-abundant 3d transition metals on the rise in catalysis

• Nikolaos Kaplaneris and
• Lutz Ackermann

Beilstein J. Org. Chem. 2022, 18, 86–88, doi:10.3762/bjoc.18.8

• these indisputable advances, this approach has, thus far, predominantly relied on precious, often toxic, 4d and 5d transition metals, most prominently palladium, rhodium and iridium. In sharp contrast, the use of less expensive and less toxic Earth-abundant 3d transition metals continues to be

• , notable advances have been accomplished with environmentally benign, Earth-abundant 3d transition metals [6][7]. The articles in this thematic issue dedicated to advances in Earth-abundant 3d metal catalysis highlight the unique power of 3d transition metals with a topical focus on homogeneous catalysis

• the editor of this issue on Earth-abundant 3d metal catalysis, it was a wonderful experience to experience the diversity of 3d transition metal catalysis, which continues to address key challenges of sustainable modern molecular syntheses. The senior author owe a great debt of gratitude to all of the

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

• and earth abundant characteristics. Moreover, much greener methodologies like microwave-assisted cyanation reactions also received much attention in recent times [21]. The cyanation can be carried out using electrophilic and nucleophilic cyanating agents [22]. Usually a cyanation is accomplished via

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

• Austin Pounder William Tam Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada 10.3762/bjoc.17.196 Abstract The development of environmentally benign, inexpensive, and earth-abundant metal

• the design of novel domino reactions. Keywords: cascade; catalysis; coupling; earth-abundant; iron; Introduction Over the past couple decades, the use of transition-metal-catalyzed cross-coupling reactions have become a staple within the organic chemist’s arsenal of carbon–carbon and carbon

• and ecological impacts have risen. This has prompted interest into the use of cheap, benign, and readily available first-row TMs [28][29][30][31][32][33][34]. A prominent earth abundant TM bringing a renaissance to the idea of green catalysis is iron. Notably, iron is the most earth-abundant d-block

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

• . Conclusion During the last decade, metallaphotoredox catalysis has emerged as an increasingly viable tool in organic synthesis for C–H functionalization. Although significant advances have been achieved with precious palladium catalysts, recently, considerable attention has been devoted to using earth

• -abundant, less toxic, and cost-effective nickel catalysts. It is clear from the wealth of the different transformations discussed in this review, the merger of photoredox catalysis and nickel catalysis offers a range of new tools for organic synthesis (Scheme 50). The impressive array of transformations

Catalyzed and uncatalyzed procedures for the syntheses of isomeric covalent multi-indolyl hetero non-metallides: an account

• Ranadeep Talukdar

Beilstein J. Org. Chem. 2021, 17, 2102–2122, doi:10.3762/bjoc.17.137

• broad applications in organic electroluminescent devices [44]. Silanes Heteroaryl compounds containing silicon, an earth abundant and non-toxic element, are important in organic electronics or photonics and in the field of drug discovery and nuclear medicine [45][46][47][48][49][50]. The first property

A new and efficient methodology for olefin epoxidation catalyzed by supported cobalt nanoparticles

• Lucía Rossi-Fernández,
• Viviana Dorn and
• Gabriel Radivoy

Beilstein J. Org. Chem. 2021, 17, 519–526, doi:10.3762/bjoc.17.46

• earth-abundant transition metals are much more attractive, especially for industrial applications [27][28]. In recent years, many efforts have been made in finding new catalytic systems based on the use of low cost and abundant non-noble metals, and much attention have been paid to the development of Fe

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• a stabilizer to control the size and distribution of the NPs and are able to intensely regulate the photocatalytic performance. 5) To improve the sustainability, noble metals need to be replaced by earth-abundant metals. However, in most cases, earth-abundant metals have a lower photocatalytic

• activity compared to noble metals in supramolecular materials. Therefore, there is an urgent demand to search for earth-abundant metals with a high activity. In conclusion, investigations on macrocycle-based catalysis are still needed to effectively extend their potential applications to solve chemical

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

• ], electron-deficient arenes [24], and nitriles [25]. Additionally, Cozzi recently applied a novel aluminium-based photocatalyst 9 to this reaction, as an earth-abundant metal alternative albeit with slightly reduced enantioselectivities (8 examples, up to 96:4 er) [26]. Interestingly, as with some other

Copper catalysis with redox-active ligands

• Agnideep Das,
• Yufeng Ren,
• Cheriehan Hessin and
• Marine Desage-El Murr

Beilstein J. Org. Chem. 2020, 16, 858–870, doi:10.3762/bjoc.16.77

• electron transfer. This review aims to present the latest results in the area of copper-based cooperative catalysis with redox-active ligands. Keywords: bioinspired catalysis; biomimetic copper complexes; cooperative catalysis; redox-active ligands; redox catalysis; Introduction Interaction of earth

• -abundant metals, such as copper, with radical ligands is originally known from biological systems such as metalloenzymes [1]. Among the myriad of existing enzymes, galactose oxidase (GAO) is a copper-based enzyme performing the two-electron oxidation of galactose through a mechanism involving the metal and

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• of these technologies has been partially hampered by the high cost and toxicity associated with Pd, in addition to the difficulty encountered when attempting to remove this metal from product mixtures. Therefore, cupper as low-cost, earth-abundant and readily available transition metal has emerged as

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• -cost metals such as copper complexes or iron complexes which will be described in detail in the paragraph below. 2.1.2 The second generation of metal-based PCs: copper and iron complexes: Due to their earth-abundant property, iron and copper have received increasing attention and development of Fe and

Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO₂ reduction

• Zhishan Luo,
• Yidong Hou,
• Jinshui Zhang,
• Sibo Wang and
• Xinchen Wang

Beilstein J. Org. Chem. 2018, 14, 2331–2339, doi:10.3762/bjoc.14.208

• Zhishan Luo Yidong Hou Jinshui Zhang Sibo Wang Xinchen Wang State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, China 10.3762/bjoc.14.208 Abstract The development of efficient, robust and earth-abundant catalysts for

• characteristics for a molecular catalyst by selective ligand modification. This work demonstrates a modulation method for fabricating effective, stable and earth-abundant molecular catalysts, which might facilitate further innovation in the function-led design and synthesis of cubane clusters for photoredox

• are typically based on noble metals (e.g., Ru, Ir) [37][38][39][40], which seriously restricts their practical applications. Therefore, the development of effective, stable and sustainable molecular catalysts based on earth-abundant elements is highly desirable [41][42][43]. Inspired by the molecular

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• Rajagopal Santhoshkumar Chien-Hong Cheng Department of Chemistry, National Tsing Hua University, Taiwan 10.3762/bjoc.14.202 Abstract As an earth-abundant first-row transition metal, cobalt catalysts offer a broad range of economical methods for organic transformations via C–H activation. One of

• or a C–H activation with high-valent cobalt to give A2 via deprotonation, followed by migratory insertion and reductive elimination or protonation (Scheme 3). We believe that this review will be helpful to the researchers for their future research on hydroarylation using earth-abundant metal

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex

• Kazuhiko Maeda,
• Daehyeon An,
• Ryo Kuriki,
• Daling Lu and
• Osamu Ishitani

Beilstein J. Org. Chem. 2018, 14, 1806–1812, doi:10.3762/bjoc.14.153

• emerging material as an organic semiconductor photocatalyst active for various kinds of reactions such as water splitting, CO2 reduction, and degradation of harmful organic compounds, because of its non-toxic, stable, and earth-abundant nature [2][3][4][5][6][7]. Our group has developed photocatalytic CO2

Thiocarbonyl-enabled ferrocene C–H nitrogenation by cobalt(III) catalysis: thermal and mechanochemical

• Santhivardhana Reddy Yetra,
• Zhigao Shen,
• Hui Wang and
• Lutz Ackermann

Beilstein J. Org. Chem. 2018, 14, 1546–1553, doi:10.3762/bjoc.14.131

• towards more sustainable base metals [10][11][12][13][14][15][16][17], with considerable progress by earth-abundant cobalt catalysts [18][19][20][21][22]. In this context, well-defined cyclopentadienyl-derived cobalt(III) complexes have proven instrumental for enabling a wealth of C–H transformations [23

Recent advances in C(sp³)–H bond functionalization via metal–carbene insertions

• Bo Wang,
• Di Qiu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2016, 12, 796–804, doi:10.3762/bjoc.12.78

• computational study of the likely intermediate suggests that it is best described as a zinc-bound carbocation rather than a zinc carbene (Scheme 12). Notably, Zn is a cheap, earth-abundant 3d metal, thus making it attractive as catalyst for C–H bond functionalization. Conclusion The intermolecular metal–carbene