Maßgeschneiderte terminale Kupfernitrene für katalytische C‐H‐Aminierungen

Moegling, Julian; Hoffmann, Alexander; Thomas, Fabian; Orth, Nicole; Liebhäuser, Patricia; Herber, Ulrich; Rampmaier, Robert; Stanek, Julia; Fink, Gerhard; Herres‐Pawlis, Sonja

doi:10.1002/ange.201713171

Cited by 7 publications

(2 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides the ligand bis(3,5‐methylpyrazolyl)pyridinylmethane [HC(3,5‐Mepz) 2 Py, L1 ] we developed the sterically more demanding compounds bis(3,5‐phenylpyrazolyl)pyridinylmethane [HC(3,5‐Phpz) 2 Py, L2 ] and bis(3,5‐ethylpyrazolyl)pyridinylmethane [HC(3,5‐Etpz) 2 Py, L3 ]. These ligands were synthesized by applying the differently modified pyrazoles in the protocol of Hoffmann et al (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

Herber

Moegling

Siris

et al. 2018

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

The ligand class of tridentate bis(pyrazolyl)methanes was extended via the syntheses of HC(3,5‐EtPz)2Py. This ligand is the first of its kind with a homogeneous 3,5‐functionalization with large substituents. On the basis of 3,5‐functionalized ligands we were able to synthesize 15 novel complexes with FeII, ZnII, and CuII salts. Herein we present an extensive coordination chemistry study, that focuses on the influences of different metals, ligands, and counterions on the coordination mode and on the spin state in case of FeII complexes.

show abstract

Section: Resultsmentioning

confidence: 99%

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

Herber

Moegling

Siris

et al. 2018

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

show abstract

“…Previously, we developed copper scorpionate complexes which are active Sonogashira catalysts in water . In principle this class of poly(pyrazolyl)methane copper complexes provides access to multiple catalytic reactions …”

Section: Introductionmentioning

confidence: 99%

One‐Pot Two‐Step Chemoenzymatic Cascade for the Synthesis of a Bis‐benzofuran Derivative

et al. 2019

Self Cite

View full text Add to dashboard Cite

Chemoenzymatic cascades enable reactions with the high productivity of chemocatalysts and high selectivity of enzymes. Nevertheless, the combination of these different fields of catalysis is prone to mutual deactivation of metal‐ and biocatalysts. In this study, a one‐pot sequential two‐step catalytic cascade reaction was successfully implemented for the synthesis of a methylene‐bridged bis(2‐substituted benzofuran). In the first step, a palladium‐free Sonogashira reaction is used for the synthesis of a benzofuran derivative. In the subsequent step, the formed 2‐substituted benzofuran is hydroxylated by the monooxygenase P450 BM3 variant (A74S‐F87V‐L188Q) and undergoes further elimination reactions. The study proofs that combination of Cu scorpionate catalyzed Sonogashira cross‐coupling and P450 mediated oxidation is possible and results in up to 84 % yield of the final product. The oxidation reaction is boosted by capturing inhibiting reaction components.

show abstract

Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

et al. 2019

View full text Add to dashboard Cite

Fluorinated bis-and tris(pyrazolyl)boratocopper complexes catalyze the nitrene insertion to CÀ H bonds of aromatic hydrocarbons efficiently producing amination products in good to excellent yields at room temperature. Imidoiodanes, PhI=NTs (Ts = p-toluenesulfonyl) and PhI=NNs (Ns = p-nitrophenylsulfonyl) serve as the nitrene source. The bis(pyrazolyl)borate catalyst [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NCMe) with PhI=NNs produced the arene CÀ H functionalized product of mesitylene in 87 % yield with only trace amounts of benzylic CÀ H insertion. The use of [H 2 B (3,5-(CF 3 ) 2 -4-(NO 2 )Pz) 2 ]Cu(NCMe) that has an even weakly donating pyrazolate generated the arene CÀ H insertion product exclusively. The tris(pyrazolyl)borate complex [HB(3,5-(CF 3 ) 2 Pz) 3 ] Cu(NCMe), in contrast, generated the benzylic amination product from mesitylene and PhI=NNs in 82 % yield with only very minor amounts of arene CÀ H functionalization. DFT calculations suggest that Cu-nitrene moiety generated from [HB (3,5-(CF 3 ) 2 Pz) 3 ]Cu(NCMe) and PhI=NNs activates the benzylic CÀ H bond of mesitylene via a hydrogen atom abstraction (HAA) followed by a radical rebound (RR) pathway, whereas the functionalization of sp 2 CÀ H bonds of mesitylene by [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NNs) ensues possibly via a nitrene addition to the arene core.[a] T.

show abstract

Maßgeschneiderte terminale Kupfernitrene für katalytische C‐H‐Aminierungen

Cited by 7 publications

References 70 publications

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

One‐Pot Two‐Step Chemoenzymatic Cascade for the Synthesis of a Bis‐benzofuran Derivative

Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

Contact Info

Product

Resources

About

Maßgeschneiderte terminale Kupfernitrene für katalytische C‐H‐Aminierungen

Cited by 7 publications

References 70 publications

A Study on FeII, ZnII and CuII Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

A Study on FeII, ZnII and CuII Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

One‐Pot Two‐Step Chemoenzymatic Cascade for the Synthesis of a Bis‐benzofuran Derivative

Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

Contact Info

Product

Resources

About

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands