Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

• growth resides in the availability of visible light-absorbing transition metal complexes. These catalysts can harvest the energy of visible-light photons and transfer it to organic molecules, giving access to key reactive intermediates. For instance, ruthenium and iridium polypyridyl complexes played a

• , the ability of transition metal complexes to intercept alkyl radicals has been exploited for expanding the possibility of C–C bond formation reactions to cross-couplings. In all of these transformations, the substituents on the alkyl radical determine if it reacts as a nucleophile or an electrophile

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• monitoring and in situ speciation. In addition, phosphine ligands have found various applications as auxiliary ligands in organometallic transition-metal complexes. A great number have exhibited potential application in organic light-emitting devices (OLEDs) [3], medicine [4][5][6] and catalysis [1][7][8

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

• electron transfer and modification of the oxidation state of the transition metal complexes. Such systems can be combined with different metals, for example, Ni, Co, Cu, Ru, Ir, etc. However, unexpectedly, copper is less toxic and can be utilized to catalyze reactions without the requirement of a ligand

• still in its infancy. Nowadays, photoredox catalysis is on the forefront as a potent strategy for bond modifications through multicatalytic strategies and the invention of nontraditional methodologies. It is enormously effective in the generation of radicals by manipulating the transition metal

• complexes and organic dyes involved [30]. Inspiring work by Pac, Kellog, Deronzier, and Sauvage on novel organic syntheses were focused on radical generation via photoredox catalysis, which has advanced C–H functionalizations to a higher level [31][32][33][34]. However, a major contribution to the

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

• corresponding bromo-cyclopropane 17 [24]. According to the authors, the passage of larger amounts of charge to facilitate product isolation might be responsible for the observed lower asymmetric yields. In 1998, Moutet’s group reported for the first time that transition metal complexes with chiral ligands can

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene

• Anna Kmieciak and
• Marek P. Krzemiński

Beilstein J. Org. Chem. 2019, 15, 2493–2499, doi:10.3762/bjoc.15.242

• research groups [1]. Compounds with a phosphorus atom attached to a stereogenic carbon center in acyclic and cyclic structures play an important role as chiral ligands in transition metal complexes [2]. They were applied to various catalytic asymmetric reactions [3][4], such as hydrogenations [3][4][5][6

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers

• Anniina Kiesilä,
• Jani O. Moilanen,
• Anneli Kruve,
• Christoph A. Schalley,
• Perdita Barran and
• Elina Kalenius

Beilstein J. Org. Chem. 2019, 15, 2486–2492, doi:10.3762/bjoc.15.241

• positive potential on the surface of the cavity, except on the N–H hydrogen atoms. They are, however, on tangential positions along the capsules surface, and therefore do not significantly contribute to anion binding [8]. More recently, we were also able to demonstrate that cationic transition metal

• complexes can template the formation of pyridinearene hexameric capsules in the gas phase [6]. Here, we report our novel findings on the ability of dimeric tetraisobutylpyridine[4]arene (compound 1 in Scheme 1) to encapsulate cationic guests. Despite of the obvious structural similarities between the

Photochromic diarylethene ligands featuring 2-(imidazol-2-yl)pyridine coordination site and their iron(II) complexes

• Andrey G. Lvov,
• Max Mörtel,
• Anton V. Yadykov,
• Frank W. Heinemann,
• Valerii Z. Shirinian and
• Marat M. Khusniyarov

Beilstein J. Org. Chem. 2019, 15, 2428–2437, doi:10.3762/bjoc.15.235

• ligand. The bridging nature of the diarylethene in the complexes prevents photocyclization. Keywords: diarylethene; 2-(imidazol-2-yl)pyridine; iron(II) complex; photochromism; Introduction Transition metal complexes with photoactive ligands are of great interest for advanced photonic applications [1][2

• ligands with pendant coordination sites were synthesized, which allowed the remote control of luminescent, nonlinear optical and magnetic properties of transition metal complexes to some extent [11][12][13][14][15][16]. However, a close arrangement of hexatriene and coordination sites is the preferred

Naphthalene diimides with improved solubility for visible light photoredox catalysis

• Barbara Reiß and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 2043–2051, doi:10.3762/bjoc.15.201

• photoredox catalytic behavior, transition metal complexes have disadvantages, including high costs due to limited availability, toxicity [22][23] and polluting properties [24]. This thwarts the principally “green” concept of photoredox catalysis. In order to avoid transition metals and enhance the

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• representative candidate of luminescent transition-metal complexes. We determined the association constants of the GC5A–dye complexes by fluorescence titration and discuss the complexation-induced photophysical changes. In addition, a comparison of the complexation behavior of GC5A with that of other macrocycles

• charge-transfer dyes. P-TPE was included in the study as a classical aggregation-induced emission (AIE) dye and TPS as a representative of a two-photon fluorescent probe. Ru(dcbpy)3 was involved as a member of luminescent transition-metal complexes. Of our special interest in the present study is to

• , higher spacial resolution and reduced photodamage of tissue [59]. The complexation of GC5A with the luminescent transition-metal complex Luminescent transition-metal complexes, especially those with ruthenium (Ru), are of great importance owing to their well-documented chemical stability, abundant

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones

• Alexander N. Reznikov,
• Anastasiya E. Sibiryakova,
• Marat R. Baimuratov,
• Eugene V. Golovin,
• Victor B. Rybakov and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2019, 15, 1289–1297, doi:10.3762/bjoc.15.127

• transition metal complexes. The preparation of hydroxy sulfones from β-ketosulfones in the presence of Ru [19][20], Ir [21] and Rh [22] complexes was described. Chiral sulfones were also obtained by hydrogenation of the C=C bond with α,β-unsaturated sulfones in the presence of Ir(I) complexes with P,N

Synthesis of polydicyclopentadiene using the Cp₂TiCl₂/Et₂AlCl catalytic system and thin-layer oxidation of the polymer in air

• Zhargolma B. Bazarova,
• Ludmila S. Soroka,
• Alex A. Lyapkov,
• Мekhman S. Yusubov and
• Francis Verpoort

Beilstein J. Org. Chem. 2019, 15, 733–745, doi:10.3762/bjoc.15.69

• interaction of organometallic transition metal complexes with organic aluminum compounds. The formation of such unstable bis(cyclopentadienyl)titanium dichloride complexes with a Ti=CHR fragment is possible as well in this case. The obtained complex is polarized in such a way that the metal has a positive

Selective benzylic C–H monooxygenation mediated by iodine oxides

• Kelsey B. LaMartina,
• Haley K. Kuck,
• Linda S. Oglesbee,
• Asma Al-Odaini and
• Nicholas C. Boaz

Beilstein J. Org. Chem. 2019, 15, 602–609, doi:10.3762/bjoc.15.55

• dyes and transition metal complexes, hypohalous acids, and persulfate anions [12][34][35][36][37][38][39][40]. An important class of catalyzed benzylic C–H to C–O transformations are those catalyzed by N-oxyl radicals. Specifically, N-oxyl radical catalysts based upon the N-hydroxyphthalimide (NHPI

Microwave-assisted synthesis of N,N-bis(phosphinoylmethyl)amines and N,N,N-tris(phosphinoylmethyl)amines bearing different substituents on the phosphorus atoms

• Erika Bálint,
• Anna Tripolszky,
• László Hegedűs and
• György Keglevich

Beilstein J. Org. Chem. 2019, 15, 469–473, doi:10.3762/bjoc.15.40

• )amines; Introduction α-Aminophosphine oxides are of considerable importance as potential precursors of α-aminophosphine ligands [1]. α-Aminophosphines play an important role in the synthesis of P(III)-transition metal complexes [2], which are often applied catalysts in homogeneous catalytic reactions [2

Reusable and highly enantioselective water-soluble Ru(II)-Amm-Pheox catalyst for intramolecular cyclopropanation of diazo compounds

• Hamada S. A. Mandour,
• Yoko Nakagawa,
• Masaya Tone,
• Hayato Inoue,
• Nansalmaa Otog,
• Ikuhide Fujisawa,
• Soda Chanthamath and
• Seiji Iwasa

Beilstein J. Org. Chem. 2019, 15, 357–363, doi:10.3762/bjoc.15.31

• diazoamide; Ru(II)-Pheox; water-soluble catalyst; Weinreb amide; Introduction Water-soluble transition metal complexes have been attracting increasing interest for catalytic applications because of their many advantages such as simple product separation, low cost, safety, and environmentally friendly

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

• traditionally carried out in the presence of transition metal complexes. In this field, 4CzIPN (Scheme 4) that was reported in the first work of Adachi et al. as a green emitter for OLEDs [69][83][84] was revisited numerous times in organocatalysis. In 2017, it was notably used for the chemoselective and

• transition metal complexes” [106]. In this mechanism, the catalyst is the most important component: it determines the equilibrium constant between the active and dormant species which is directly linked to the distribution of chain lengths [107]. As photoredox catalysts for ATRP applications, copper(II

Reactions of 3-(p-substituted-phenyl)-5-chloromethyl-1,2,4-oxadiazoles with KCN leading to acetonitriles and alkanes via a non-reductive decyanation pathway

• Akın Sağırlı and
• Yaşar Dürüst

Beilstein J. Org. Chem. 2018, 14, 3011–3017, doi:10.3762/bjoc.14.280

• ], transition metal complexes [25], and alkali metals in a variety of solvents [26]. Generally, they require mostly an inert atmosphere as well as harsh reaction conditions. These facts constitute challenges to the development of mild reaction conditions in the reduction of nitrilated compounds. In the light of

The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study

• Magdalena Jawiczuk,
• Angelika Janaszkiewicz and
• Bartosz Trzaskowski

Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266

• recently and examples of their transition metal complexes are scarce. In 2013 Ganter described a cationic NHC with a fused pyridinium moiety and the formal +1 charge just one bond away from the imidazole core [27]. In 2017 César synthesized a cationic imidazolylidene NHC with an ammonium tag attached

• interesting phenomenon, despite its very limited impact on their propensity to form transition metal complexes (Scheme 2) [50]. Many works have been devoted to the study of carbene dimerization and present evidence that mechanism of monomer–dimer equilibrium depends on the balance between the electronic and

DABCO- and DBU-promoted one-pot reaction of N-sulfonyl ketimines with Morita–Baylis–Hillman carbonates: a sequential approach to (2-hydroxyaryl)nicotinate derivatives

• Soumitra Guin,
• Raman Gupta,
• Debashis Majee and
• Sampak Samanta

Beilstein J. Org. Chem. 2018, 14, 2771–2778, doi:10.3762/bjoc.14.254

• products [4], medicines [5], chelating agents in transition metal complexes [6][7], and material science [8][9]. Pyridine derivatives such as vitamins B6, B3 (niacin), and nicotinamide adenine dinucleotide (NAD) play a significant role in the metabolism process of living organisms. Consequently, many

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

• Cristina Cebrián and
• Matteo Mauro

Beilstein J. Org. Chem. 2018, 14, 1459–1481, doi:10.3762/bjoc.14.124

• organometallic compounds based on heavy transition metal complexes (TMCs) are an appealing research topic of enormous current interest. Amongst all different fields in which they found valuable application, development of emitting materials based on TMCs have become crucial for electroluminescent devices such as

AuBr₃-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars

• Jayashree Rajput,
• Srinivas Hotha and
• Madhuri Vangala

Beilstein J. Org. Chem. 2018, 14, 682–687, doi:10.3762/bjoc.14.56

• -benzoylated disaccharides needed 2–3 h of heating at 55 °C. Keywords: acylated sugars; azidation; gold(III) bromide; N-glycoside; oxophilicity; Introduction The past few decades had seen the enrichment of transition metal complexes in various glycosylation strategies [1]. In particular, gold complexes with

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• % for phosphorescent OLEDs [5]. As drawback, triplet emitters are transition-metal complexes mostly based on iridium, platinum and osmium and the scarcity of these metals on Earth, their toxicity and high cost make these materials unsuitable candidates for a mass-production of OLEDs [6]. However

Pd(OAc)₂/Ph₃P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

• Dominik Kellner,
• Maximilian Weger,
• Andrea Gini and
• Olga García Mancheño

Beilstein J. Org. Chem. 2017, 13, 1807–1815, doi:10.3762/bjoc.13.175

• formed: tail-to-tail, head-to-tail, tail-to-head and head-to-head (Figure 1). In addition to the linear dimeric products, cyclic monoterpenes such as limonene can also be formed as byproducts. A number of transition metal complexes can be used as catalysts in the dimerization of isoprene. In one hand

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• diesters: In 1951, Gilmore has demonstrated that use of esters, rather than free arylpropionic acids in phosphoric acid, in the presence of phosphorus pentoxide also led to 1-indanones in equally good or even better yields [32]. Transition metal complexes have been used by Negishi et al. as catalysts in

• using lithium, nickel and palladium catalysts (Scheme 15). A general mechanism illustrating the role of transition metal complexes and CO in this reaction is shown in Scheme 15. Cyclic esters were also used in the syntheses of 1-indanones. Thus, by adding β-propiolactone to aluminum chloride in benzene

Organometallic chemistry

• Bernd F. Straub,
• Rolf Gleiter,
• Claudia Meier and
• Lutz H. Gade

Beilstein J. Org. Chem. 2016, 12, 2216–2221, doi:10.3762/bjoc.12.213

• studied the electronic structure of organo-transition metal complexes by extended Hückel model calculations [14][17][20][28][39][49][50][54][57]. In 1978, he completed his habilitation in Erlangen, mentored by Paul von Ragué Schleyer, and was promoted to professor in 1980. Following a three-month visiting

• the very few chemists with a history of research and teaching in theoretical, organic and inorganic chemistry. His research interests combined all three fields, with a focus on homogeneous catalysis with transition metal complexes. Bidentate donor ligands with a small bite angle such as bis(di-tert

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• . Finally, the decomposition of 62 gives esters 59a–f. A number of other modern oxidizing systems are based on transition metal-peroxo complexes. The use of transition metal complexes were also used as catalysts for the Baeyer–Villiger reaction and the first example was documented in 1978 [196][214]. For

• example, Mo(VI) peroxo complexes 64 and 65 were employed as the catalysts and 90% H2O2 served as the oxidizer (Table 5). The results obtained from the reactions using molybdenum systems have stimulated the search for new catalysts based on transition metal complexes. The usage of the platimum complex