Bio-organometallic Organosulfur Chemistry. Transi- tion Metal-Catalyzed Cross-Coupling Using Coen- zyme M or Thioglycolic Acid as the Leaving Group

Šrogl, Jiří; Liu, Wansheng; Marshall, D. H.; Liebeskind, Lanny S.

doi:10.1021/ja991654e

Cited by 99 publications

(44 citation statements)

References 34 publications

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“…In 1999, the rst example of such a Negishi type transformation was reported by Liebeskind (Scheme 1). 5 In this report, the cross coupling reaction of aryl sul des with diarylzincs was accomplished by means of chelating thioglycolic acid as a specially designed leaving group that captures a zinc ion to facilitate transmetalation. After this nding, several Negishi type coupling reactions of aryl sul des were developed, though the aryl groups must be activated heteroaryls such as thioester mimics (2 pyridyl, 2 pyrimidyl, etc.…”

Section: With Organozinc Reagentsmentioning

confidence: 99%

Cross-coupling of Aryl Sulfides Powered by N-Heterocyclic Carbene Ligands

Gao¹,

Otsuka²,

Baralle³

et al. 2016

J. Synth. Org. Chem. Jpn.

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Cross coupling reactions of aryl sul des are more dif cult than they look. We have disclosed that transition metal NHC complexes allow us to ef ciently use a wide range of aryl sul des as electrophilic coupling partners in various cross coupling reactions and have thus signi cantly expanded the scope of aryl suldes available for the cross coupling technology. Newly introduced nucleophilic partners include arylzinc reagents, Grignard reagents such as alkynylmagnesium species, amines, ketimines, and diborons to achieve Negishi type coupling, Kumada Tamao Corriu type coupling, Buchwald Hartwig type amination, Buchwald Hartwig Miura type carbonyl α arylation, and Miyaura type borylation, respectively. These cross coupling reactions are particularly advantageous when combined with sulfur speci c transformations to prepare organosulfur substrates. Through the development of catalytic transformations of C S bonds, sulfur based organic synthesis has come to complement conventional halogen based organic methodology.

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Section: With Organozinc Reagentsmentioning

confidence: 99%

Cross-coupling of Aryl Sulfides Powered by N-Heterocyclic Carbene Ligands

Gao¹,

Otsuka²,

Baralle³

et al. 2016

J. Synth. Org. Chem. Jpn.

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“…An efficient and general coupling ensued (Scheme 2); examples can be found in the published manuscript [18].…”

Section: Biomimetic Cross-couplingmentioning

confidence: 99%

Bioinspired organometallic chemistry

Liebeskind

Šrogl

Savarin

et al. 2002

Pure and Applied Chemistry

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Given the stability of the bond between a mercaptide ligand and various redoxactive metals, it is of interest that Nature has evolved significant metalloenzymatic processes that involve key interactions of sulfur-containing functionalities with metals such as Ni, Co, Cu, and Fe. From a chemical perspective, it is striking that these metals can function as robust biocatalysts in vivo, even though they are often "poisoned" as catalysts in vitro through formation of refractory metal thiolates. Insight into the nature of this chemical discrepancy is under study in order to open new procedures in synthetic organic and organometallic chemistry.

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“…The complexes displayed interesting electrochemical properties and higher antimicrobial activity compared with the commercially available antibiotics, and have found application in various areas such as catalysts in crosscoupling reactions and medicine. [8][9][10][11] They are also used as effective light stabilizers for olefins, 12 and recently as precursors for the preparation of nanoparticles. 13 Ni(II) complexes do not stabilize their geometries effectively under various chemical environments.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structure, thermal and theoretical studies of bis(N-ethyl-N-phenyldithiocarbamato) Ni(II) and (N-ethyl-N-phenyldithiocarbamato) (isothiocyanato) (triphenylphosphine) Ni(II)

et al. 2016

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Homoleptic and heteroleptic Ni(II) complexes represented as NiL 1 2 and NiL 1 L 2 L 3 (where, L 1 = N -ethyl-N -phenyldithiocarbamato anion, L 2 = isothiocyanato anion, and L 3 = triphenylphosphine) were synthesized. The complexes have been characterized by elemental, IR, NMR, and single-crystal X-ray analysis. The thermal decomposition behaviour of the complexes were studied using thermogravimetric analysis (TGA). The optimized geometry and the electronic analysis of the type of bonding within the complex structures were performed using methods based on the density functional theory and atom in molecule (AIM) analysis method. X-ray structural analysis of both complexes confirms distorted square planar geometry about the Ni atom. The TGA indicates that the complexes belong to the class of volatile dithiocarbamates which yield the corresponding metal sulphide without any intermediate products. Structural parameters from crystallographic and DFT studies have been compared and found to correlate with each other. The small discrepancies in geometric parameters are attributable to H-bonding and packing interactions within the lattice which are not modelled during computational study. AIM analysis suggests that in NiL 1 L 2 L 3 , the Ni· · · L interactions are more covalent in nature whereas in NiL 1 2 complex, they are more ionic in character.

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Bio-organometallic Organosulfur Chemistry. Transi- tion Metal-Catalyzed Cross-Coupling Using Coen- zyme M or Thioglycolic Acid as the Leaving Group

Cited by 99 publications

References 34 publications

Cross-coupling of Aryl Sulfides Powered by <i><b>N</b></i>-Heterocyclic Carbene Ligands

Cross-coupling of Aryl Sulfides Powered by <i><b>N</b></i>-Heterocyclic Carbene Ligands

Bioinspired organometallic chemistry

Synthesis, crystal structure, thermal and theoretical studies of bis(N-ethyl-N-phenyldithiocarbamato) Ni(II) and (N-ethyl-N-phenyldithiocarbamato) (isothiocyanato) (triphenylphosphine) Ni(II)

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