Recent Catalytic Applications of Ferrocene and Ferrocenium Cations in the Syntheses of Organic Compounds.

Ferrocene and its oxidized counterpart, the ferrocenium cation, represent a fascinating class of organometallic compounds with broad utility across various fields, including organic synthesis, pharmaceuticals, and materials science. Over the years, ferrocene, ferrocenium cations, and their derivatives have also gained prominence for their versatility in catalytic processes. This review article offers an overview of the research of the last decade into ferrocene- and ferrocenium-based catalysis.

Ferrocenophanium Stability and Catalysis.

Ferrocenium catalysis is a vibrant research area, and an increasing number of ferrocenium-catalyzed processes have been reported in the recent years. However, the ferrocenium cation is not very stable in solution, which may potentially hamper catalytic applications. In an effort to stabilize ferrocenium-type architectures by inserting a bridge between the cyclopentadienyl rings, we investigated two ferrocenophanium (or -ferrocenium) cations with respect to their stability and catalytic activity in propargylic substitution reactions.

Ferrocenium complex aided -glycosylation of glycosyl halides.

A new strategy for the activation of glycosyl halide donors to be utilized in glycosylation reactions is presented, utilizing the ferrocenium (Fc) complexes [FcB(OH)]SbF and FcBF as promoters. The scope of the new system has been investigated using glycosyl chloride and glycosyl fluoride donors in combination with common glycosyl acceptors, such as protected glucose. The corresponding glycosylation products were formed in 95 to 10% isolated yields with / ratios ranging from 1/1 to only (2 to 14 h reaction time at room temperature, 40 to 100% ferrocenium promoter load).

Transition metal catalyzed glycosylation reactions - an overview.

Carbohydrates are a large class of natural products that play key roles in a number of biological processes such as in cellular communication or disease progression. Carbohydrates are also used as vaccines and pharmaceuticals. Their synthesis through glycosylation reactions is challenging, and often stoichiometric amounts of promoters are required.

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts.

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes.

Chemoselective, iron(II)-catalyzed oxidation of a variety of secondary alcohols over primary alcohols utilizing H2O2 as the oxidant.

A mild, iron-based catalyst system is presented that selectively oxidizes secondary alcohols to the corresponding hydroxy ketones in the presence of primary alcohols within 15 minutes at room temperature, utilizing H2O2 as the oxidant.

Chiral-at-metal complexes and their catalytic applications in organic synthesis.

This tutorial review provides an introduction to the synthesis and characterization of chiral-at-metal complexes and their catalytic application in organic transformations. The synthetic access to these architectures either via chiral resolution or by employment of chiral ligands is described, characterization techniques for the complexes are referenced and the application of the R/S nomenclature is explained. Racemization and epimerization processes are often observed for the title compounds; the article gives mechanistic insights to these processes and describes how to recognize and document them.

New iron(II) α-iminopyridine complexes and their catalytic activity in the oxidation of activated methylene groups and secondary alcohols to ketones.

A set of iron(II) complexes of the general formula [Fe(OTf)(2)L(2)] was synthesized in 32 to 78% isolated yields, where L represents a bidentate α-iminopyridine ligand. Four of the iron complexes were characterized structurally, revealing a rich coordination chemistry, because the coordination geometry of the iron complexes strongly depends on the substitution pattern exhibited by the ligands L. The catalytic activity of the new complexes was demonstrated in the oxidation of cyclohexane, activated methylene groups and secondary alcohols to the corresponding ketones utilizing H(2)O(2) and t-BuOOH as the oxidants.

New chiral phosphoramidite complexes of iron as catalytic precursors in the oxidation of activated methylene groups.

New phosphoramidite complexes of iron were synthesized and structurally characterized. Reaction of the known chiral phosphoramidites (RO)2PNR'2 (R = binaphthyl, R' = CH3, 1a; R = binaphthyl, R' = benzyl, 1b) with [FeBr(Cp)(CO)2] afforded the title compounds [FeBr(Cp)(CO)(1a,b)] (4a,b) in 34 and 65 % isolated yields as mixtures of diastereomers, since both the metal and the ligand are stereogenic. Similarly, reaction of 1b with [Fe(Cp)I(CO)2] in the presence of catalytic [Fe(Cp)(CO)2]2 afforded [Fe(Cp)I(CO)(1b)] (5b) in 81% yield as a mixture of diastereomers.

Air- and water-stable catalysts for hydroamination/cyclization. Synthesis and application of CCC-NHC pincer complexes of Rh and Ir.

The scope of CCC-NHC pincer complex synthetic methodology by metalation/transmetalation has been extended to Ir. Structural characterization revealed that it is isomorphous with the Rh complex. Both Rh and Ir complexes are efficient catalysts for the hydroamination/cyclization of secondary amines in the presence of air and/or water.

sp carbon chains surrounded by sp(3) carbon double helices: directed syntheses of wirelike Pt(CC)(n)Pt moieties that are spanned by two P(CH(2))(m)P linkages via alkene metathesis.

Reactions of trans-(C6F5)(Ph2P(CH2)m'CH=CH2)2PtCl (1; m' = a, 6; b, 7; c, 8; d, 9; e, 10) and H(CC)2H (HNEt2, cat. CuI) give trans-(C6F5)(Ph2P(CH2)m'CH=CH2)2Pt(CC)2H (3a-e, 80-95%). Oxidative homocouplings of 3a-d under Hay conditions (O2, cat.

Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands.

The alkene-containing phosphines PPh((CH2)(n)CH=CH2)2)2 are prepared from PPhH(2), n-BuLi, and the corresponding bromoalkenes (1:2:2), and combined with the platinum tetrahydrothiophene complex [Pt(mu-Cl)(C(6)F(5))(S(CH2CH2(-))2)]2 to give the square-planar adducts trans-(Cl)(C(6)F(5))Pt(PPh((CH2)(n)CH=CH2)2)2 (11, 93-73%; n=a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With, two isomers of trans-(Cl)(C6F5)[formula: see text](14)Ph)(15e) are isolated after hydrogenation.