Selective C–F and C–H Activation of Fluoroarenes by Fe(PMe<sub>3</sub>)<sub>4</sub> and Catalytic Performance of Iron Hydride in Hydrosilylation of Carbonyl Compounds

We herein describe for the first time that an optimized combination of Zn and NH4Cl can be used for the selective reduction of aldehydes and ketones to the corresponding alcohols. The aldehyde and keto groups are selectively reduced in the presence of azide, cyano, epoxy, ester, and carbon–carbon double‐bond functional groups. A broad functional‐group compatibility, chemoselective reduction of aldehydes in the presence of ketones, and selective reduction of isatins at the C3 carbonyl group are the highlights of the present method.

show abstract

“…Cyclopentanol (5p): According to GP‐II, cyclopentanone ( 4q ) (84 mg, 1.0 mmol, 1.0 equiv.) afforded 5p (64 mg, 74 %) as a colorless liquid.…”

Section: Methodsmentioning

confidence: 99%

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

Mandal

Jana

2017

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…Thus, they reported the use of cyclometalated iron complexes such as the hydrido iron complex C171 as a catalyst (0.3–0.6 mol %) in the presence of 1.2 equiv of (EtO) 3 SiH in THF at 55 °C for the reduction of aldehydes and ketones yielding the alcohols in 65–92% (Scheme ). Other similar iron hydride complexes like C172 , C173 , C174 , and C175 , , were also applied in hydrosilylation reactions under similar conditions giving comparable activities (Scheme ).…”

Section: Hydrosilylationmentioning

confidence: 96%

Iron Catalysis in Reduction and Hydrometalation Reactions

2018

View full text Add to dashboard Cite

The last two decades have seen an impressive improvement of the use of iron as a fascinating and valuable alternative transition metal in homogeneous catalysis in terms of sustainability and economy. It was efficiently used in catalytic organic synthetic transformations, which in particular include the reduction of unsaturated bonds. This review summarizes the fast development and the recent advances in selective reductions of olefins, alkynes, carbonyl and carboxylic derivatives, imines, and nitro compounds promoted by iron catalysts. The topical hydrogen-borrowing reactions and hydroboration of unsaturated compounds are also reported. It is hoped that this account not only provides an overview of the state of the art in iron catalysis but also stimulates the development of superior greener catalytic systems in the near future.

show abstract

“…Very recently, Tauchert and co-workers reported a palladium(0) complex supported by a Z-type Zn(II)-based ligand, which displayed high activity in the hydrosilylation of carbon dioxide . In addition, metal-catalyzed hydrosilylation of carbonyl substrates using silanes offers an efficient protocol for the reduction of aldehydes . With the bimetallic Zn–Pd complex 5b in hand, this compound was subsequently tested for the hydrosilylation of aromatic aldehydes by using Ph 2 SiH 2 and PhSiH 3 as reducing reagents.…”

Section: Results and Discussionmentioning

confidence: 99%

Formation of Zn–Zn and Zn–Pd Bonded Complexes by Reactions of Terminal Zinc Hydrides with Pd(II) Species

Jiang

Chen

2019

Inorg. Chem.

View full text Add to dashboard Cite

Divalent palladium-induced homocoupling of terminal zinc hydrides to zinc−zinc bonded complexes was achieved herein. Reactions of zinc hydrides [LZnH] (L = CH 3 C(2,6-i Pr 2 C 6 H 3 N)CHC(CH 3 )(N(CH 2 ) n CH 2 PPh 2 ); 1a: n = 1; 1b: n = 2) with 0.5 equiv of allyl(cyclopentadienyl)palladium(II) afforded heterotrinuclear [Zn 2 Pd] complexes 3 containing direct Zn−Zn and Zn−Pd bonds, with concomitant elimination of propylene and cyclopentadiene. Complexes 3 were also accessed by the reactions of zinc hydrides 1 with allylpalladium(II) chloride with release of propylene and hydrogen chloride. Treatment of zinc hydrides 1 with 1 equiv of allyl(cyclopentadienyl)palladium(II) gave Zn−Pd bonded complex 5 by elimination of propylene, which can be transformed into heterotrinuclear complex 3 by further reaction with one additional molar equivalent of zinc hydrides. Heterobimetallic Zn−Pd complex 5b was found to be an effective catalyst in the hydrosilylation of benzaldehyde and its derivatives. Reaction of 5b with silane reagent Ph 2 SiH 2 produced [Pd 2 Si 2 H 2 ] complex 8 with cleavage of the Pd−Zn bond, which served as an initiating species in the catalytic reaction. Complexes 4b, 5, and 8 in this study were characterized by X-ray diffraction.

show abstract

Selective C–F and C–H Activation of Fluoroarenes by Fe(PMe₃)₄ and Catalytic Performance of Iron Hydride in Hydrosilylation of Carbonyl Compounds

Abstract: Stick/ball representations and Cartesian coordinates of complexes 1 and 3(2) IR spectra of complexes 1 -4 and 6(3) 1 H NMR, 31 P NMR, 19 F NMR and 13 C NMR spectra of complexes 4 and 6 (4) 1 H NMR and 13 C NMR spectra of the catalytic products (alcohols)

Cited by 23 publications

References 77 publications

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

Iron Catalysis in Reduction and Hydrometalation Reactions

Formation of Zn–Zn and Zn–Pd Bonded Complexes by Reactions of Terminal Zinc Hydrides with Pd(II) Species

Contact Info

Product

Resources

About

Selective C–F and C–H Activation of Fluoroarenes by Fe(PMe3)4 and Catalytic Performance of Iron Hydride in Hydrosilylation of Carbonyl Compounds

Abstract: Stick/ball representations and Cartesian coordinates of complexes 1 and 3(2) IR spectra of complexes 1 -4 and 6(3) 1 H NMR, 31 P NMR, 19 F NMR and 13 C NMR spectra of complexes 4 and 6 (4) 1 H NMR and 13 C NMR spectra of the catalytic products (alcohols)

Cited by 23 publications

References 77 publications

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

Iron Catalysis in Reduction and Hydrometalation Reactions

Formation of Zn–Zn and Zn–Pd Bonded Complexes by Reactions of Terminal Zinc Hydrides with Pd(II) Species

Contact Info

Product

Resources

About

Selective C–F and C–H Activation of Fluoroarenes by Fe(PMe₃)₄ and Catalytic Performance of Iron Hydride in Hydrosilylation of Carbonyl Compounds