Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• diastereomerically pure γ‑branched fluorinated amino acids. This work further underlines the importance of chiral Ni(II) complexes in the synthesis of fluorinated amino acids. Keywords: chiral nickel complexes; fluorinated amino acids; gram-scale amino acid synthesis; stereoselective synthesis; Introduction Non

• chiral nickel complexes. In recent years, the Soloshonok working group demonstrated the synthesis of non‑natural amino acids using the corresponding chiral Ni(II) complex [7]. In addition to the high enantiomeric purity of the corresponding products, the scale of the reaction, which extends into the

• the repertoire of published syntheses for this fluorinated derivative of natural leucine. Further attempts to the isolation of the second isomer will be made. Overall, this work further underlines the potential of chiral nickel complexes in synthesizing fluorinated amino acids. The diverse range of

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

• complex compounds (Scheme 35). In addition, Niu and coworkers reported a similar work on a cobalt-electrocatalyzed atroposelective C–H annulation of benzamides with acetylenes [48]. 1.3.3 Ni-assisted anodic oxidation: Apart from cobalt, nickel complexes have also been applied in anionic oxidations and

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• catalytic approaches [9]. Especially the combination with other transition metal catalysts (metallaphotoredox catalysis), such as nickel complexes, resulted in a vast number of new methods to achieve cross-couplings under mild conditions [10]. However, the conditions of these methods are often hard to

• combination of solid photocatalysts (i.e., semiconductors) and homogeneous nickel complexes are feasible, but the fact that the nickel complex is in solution reduces the benefits of packed-bed reactor types [19][23][24]. Recently, several bifunctional heterogeneous catalysts that combine the photo- and the

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

• were thus obtained with good enantioselectivity. In the same year, Kim’s group [97] accomplished an efficient enantioselective electrophilic α-fluorination of various α-chloro-β-ketoesters catalyzed by chiral nickel complexes with good enantioselectivity (up to 99% ee). Notably, the chiral nickel

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

• ; Michael addition; nickel complexes; nitroalkenes; Introduction Sulfones are widely used in organic synthesis, particularly, in various reactions of C–C and C=C-bond formation [1][2][3][4]. The use of sulfones in Julia–Kocienski [1] and Ramberg–Bäcklund reactions [2] made this class of compounds

Coordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands

• Jennifer Klose,
• Tobias Severin,
• Peter Hahn,
• Alexander Jeremies,
• Jens Bergmann,
• Daniel Fuhrmann,
• Jan Griebel,
• Bernd Abel and
• Berthold Kersting

Beilstein J. Org. Chem. 2019, 15, 840–851, doi:10.3762/bjoc.15.81

• distance between the two planes through the co-ligands amounts to 3.45 Å. Magnetic properties of nickel complexes The paramagnetic nickel complexes 2, 4, and 7 were further investigated by temperature dependent magnetic susceptibility measurements between 2 and 300 K in an applied external field of 0.5 T

• the parent benzene chromophore utilizing Clar’s notation [26], assuming that the electron-donating alkyl and thiol substituents exert a bathochromic effect. The spectral properties of the nickel complexes differ from those of the zinc and cadmium counterparts in that they exhibit two additional

From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer

• Ming Liu,
• Jan C. Namyslo,
• Martin Nieger,
• Mika Polamo and
• Andreas Schmidt

Beilstein J. Org. Chem. 2016, 12, 2673–2681, doi:10.3762/bjoc.12.264

• ) chloride at reflux temperature resulted in the formation of the nickel complex [Ni(7)2] (12, Scheme 2). Single crystals were obtained by slow evaporation of 12 from EtOAc/MeOH. The X-ray analysis shows two independent nickel complexes which are connected via hydrogen bonds to two water molecules (Figure 5

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

• Carmen Mejuto,
• Beatriz Royo,
• Gregorio Guisado-Barrios and
• Eduardo Peris

Beilstein J. Org. Chem. 2015, 11, 2584–2590, doi:10.3762/bjoc.11.278

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

• Johnathon Yau,
• Kaarel E. Hunt,
• Laura McDougall,
• Alan R. Kennedy and
• David J. Nelson

Beilstein J. Org. Chem. 2015, 11, 2171–2178, doi:10.3762/bjoc.11.235

• -coupling; N-heterocyclic carbenes; nickel; Introduction Nickel catalysis is currently an area of great interest, due to the potential for nickel to replace palladium in some catalytic processes, as well as its ability to perform a much wider range of reactions [1]. Nickel complexes bearing N-heterocyclic

(2R,1'S,2'R)- and (2S,1'S,2'R)-3-[2-Mono(di,tri)fluoromethylcyclopropyl]alanines and their incorporation into hormaomycin analogues

• Armin de Meijere,
• Sergei I. Kozhushkov,
• Dmitrii S. Yufit,
• Christian Grosse,
• Marcel Kaiser and
• Vitaly A. Raev

Beilstein J. Org. Chem. 2014, 10, 2844–2857, doi:10.3762/bjoc.10.302

• (2R,1'R,2'S)-26b were determined by a single crystal X-ray structure analysis (see Figure 3 and Supporting Information File 1) [28]. The isolated nickel complexes 26a–c were decomposed by treatment with refluxing aqueous methanolic hydrogen chloride to give, after ion-exchange chromatography, the

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• hydrophosphinations. Metal complex-catalyzed hydrophosphinations Hydrophosphination catalysts are mainly based on transition metals. However, it has been shown that lanthanides and alkaline earth metals can offer a valid alternative. Palladium and nickel complexes were used to catalyze the addition of the P–H bond to

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• discussed for its Pd-catalyzed variant, is also catalyzed by nickel complexes (Scheme 11) [71]. Actually, the nickel-based systems provided higher yields than the palladium-based one (see section 3.1.3). Considering control voltamperometric experiments, a Ni(II)/Ni(III) catalytic cycle seemed to be

Micro-flow synthesis and structural analysis of sterically crowded diimine ligands with five aryl rings

• Shinichiro Fuse,
• Nobutake Tanabe,
• Akio Tannna,
• Yohei Konishi and
• Takashi Takahashi

Beilstein J. Org. Chem. 2013, 9, 2336–2343, doi:10.3762/bjoc.9.268

• , Yokohama 227-8502, Japan 10.3762/bjoc.9.268 Abstract Sterically crowded diimine ligands with five aryl rings were prepared in one step in good yields using a micro-flow technique. X-ray crystallographic analysis revealed the detailed structure of the bulky ligands. The nickel complexes prepared from the

• chelate plane probably due to the strong steric repulsions among the aryl rings. The tetrahedral geometry around nickel was distorted similar to the previously reported nickel complexes of 2b, 2f and 2g [18][19]. For example, Br(1) was almost perpendicular to the plane of the metal-containing ring. This

• = 6.8, 1H); FTIR (neat) 3056, 1631, 1595, 1524, 1497, 1438, 1323, 775, 698 cm−1; HRMS (ESI–TOF, m/z): [M + H]+ calcd. for C40H30N3, 552.2440; found, 552.2435. General procedure for the preparation of nickel complexes 12 and 13 The following manipulations were performed under an inert atmosphere using