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Epoxidized vegetable oils (EVOs) are versatile building blocks for lubricants, plasticizers, polyvinyl chloride (PVC) stabilizers, and surface coating formulations. In this paper, a catalytic protocol for the efficient epoxidation of vegetable oils is presented that is based on a combination of a manganese catalyst, H 2 O 2 as an oxidant, and acetic acid as an additive. This protocol relies on the use of a homogeneous catalyst based on the non-noble metal manganese in combination with a racemic mixture of the N,N′-bis(2-picolyl)-2,2′-bispyrrolidine ligand (rac-BPBP). The optimized reaction conditions entail only 0.03 mol% of the manganese catalyst with respect to the number of double bonds (ca. 0.1 wt% with respect to the oil) and ambient temperature. This epoxidation protocol is highly efficient, since it allows most of the investigated vegetable oils, including cheap waste cooking oil, to be fully epoxidized to EVOs in more than 90% yield with excellent epoxide selectivities (>90%) within 2 h of reaction time. In addition, the protocol takes place in a biphasic reaction medium constituted by the vegetable oil itself and an aqueous acetic acid phase, from which the epoxidized product can be easily separated via simple extraction. In terms of efficiency and reaction conditions, the current epoxidation protocol outperforms previously reported catalytic protocols for plant oil epoxidation, representing a promising alternative method for EVO production.

Trioxo‐rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass‐derived polyols using CpttReO3 as a new catalyst (Cptt=1,3‐di‐tert‐butylcyclopentadienyl). The DODH reaction was optimized using 2 mol % of CpttReO3 and 3‐octanol as both reductant and solvent. The CpttReO3 catalyst exhibits an excellent activity for biomass‐derived polyols. Specifically, glycerol is almost quantitatively converted to allyl alcohol and mucic acid gives 75 % of muconates at 91 % conversion. In addition, the loading of CpttReO3 can be reduced to 0.1 mol % to achieve a turn‐over number as high as 900 per Re when using glycerol as substrate. Examination of DODH reaction profiles by NMR spectroscopy indicates that catalysis is related to Cp‐ligand release, which raises questions on the nature of the actual catalyst.

A system of three coupled catalytic cycles enabling the one-pot transformation of epoxides to amines via Meinwald rearrangement, imine condensation, and imine reduction is described. This assisted tandem catalysis is catalyzed by B(C6F5)3 resulting in the first tandem Meinwald rearrangement-reductive amination protocol. The reaction proceeds in nondried solvents and yields β-functionalized amines. In particular, β-diarylamines are obtained in high yields.

Iron complexes derived from a bis-isoindoline-bis-pyridine ligand platform based on the BPBP ligand (BPBP = N,N′-bis(2-picolyl)-2,2′-bis-pyrrolidine) have been synthesized and applied in selective aliphatic C–H oxidation with hydrogen peroxide under mild conditions. The introduction of benzene moieties on the bis-pyrrolidine backbone leads to an increased preference of tertiary over secondary C–H bond oxidation (3°/2° ratio up to 33). On the other hand, substituting the meta-position of the pyridines with bulky silyl groups affords enhanced secondary C–H oxidation selectivity and generally leads to higher product yields and mass balances.

The selective synthesis of purely organic cages withhetero-sequenced functionalized cavities is demonstrated. Thestrategy to obtain these compounds is based on a stepwiseapproach using thermodynamically controlled imine condensa-tions. To accomplish this, the amine building blocks carry addi-tional azide groups, which act as masked amines and enablethe synthesis of the desired cavities. This approach offers a precise control of interior functionalization, the substitution pat-tern and the cage size, which is demonstrated by the selectivesynthesis of four cages. The largest described cage has beeninvestigated towards its ability for guest encapsulation and isable to selectively encapsulate functionalized arenes that offera matching substitution pattern.

Mononuclear iron(II) complexes with facially coordinating N,N,O-ligands were synthesized as accurate structural mimics of the 2-His-1-carboxylate facial triad found in mononuclear non-heme iron enzymes. Mimicking of the facial triad is achieved by designing sterically demanding ligands providing two histidine-like benzimidazole moieties and a coordinating carboxylate or ester moiety. The new methyl-substituted analogue of the bis(benzimidazolyl)propionate ligand, BMBMeIP and its ester analogue, BMBMeIPnPr are designed to prevent the formation of previously reported coordinatively saturated FeL2 type complexes. The crystal structure of [Fe(BMBMeIPnPr)(OTf)2] shows a facial N,N,O-coordination that is very similar to the structure of the enzyme active sites. Both [Fe(BMBMeIPnPr)(OTf)2] and [Fe(BMBMeIP)(OTf)(MeCN)n] catalyze the epoxidation of olefins using H2O2, reaching turnover numbers up to 5.8 per iron. These results represent the first examples of iron complexes bearing a single facial and rigid N,N,O-coordinating ligand and three readily available coordination sites showing catalytic activity in oxidation reactions.

The first shape-persistent macrocycle 1 offering a Brønsted pair functionalized interior is described. Via postcyclization transformation, this heterosequenced compound can be obtained from its corresponding ester 2. The macrocycles differ dramatically in their characteristics such as solubility and appearance. Theoretical investigations suggest that those contrasts might originate from conformational changes due to the formation of a strong O-H-N hydrogen bond in 1.

A method for the regioselective transformation of dienes to carbonyl compounds has been developed. Electron-rich olefins react selectively to yield valuable aldehydes and ketones. The method is based on the catalyst [Fe(OTf)2(mix-BPBP)] with an oxidant combination of H2O2 (1.0 equiv.) and NaIO4 (1.5 equiv.); it uses mild conditions and short reaction times, and it outperforms other olefin cleavage methodologies. The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0-50 C) and short reaction times (70 min).

The role of toroidal plasma currents for the island divertor scrape-off layer in the stellarator Wendelstein 7-X is investigated using reciprocating electric probes. Experiments show that small amounts (of a few kA) of plasma current are sufficient to significantly affect the scrape-off layer plasma conditions, whereas higher plasma currents above 10kA result in more drastic changes. This behavior is linked to the effect of the plasma current on the rotational transform profile, which can result in significant shifts of the edge magnetic islands. These shifts affect the interaction of the islands with the divertor and can eventually result in a transition from a diverted to a limited plasma configuration. The probe observations are complemented by further edge diagnostics including plasma flow measurements, divertor Langmuir probes, divertor thermography and impurity spectroscopy.

C–H and C=C bond oxidations constitute essential transformations in organic synthesis and in many biological and industrial processes. In the past decades numerous non-heme iron enzymes have been discovered and identified, that are able to conduct biological C–H and C=C bond oxidations via O2 activation in a very selective manner. Inspired by these enzymes, many efforts have been spent on modelling catalytic iron sites and active intermediates involved in catalysis, in order to achieve these oxidation reactions by molecular catalysts outside the enzyme environment. Depending on the ligand, the coordination chemistry and reactivity of synthetic non-heme iron complexes may be drastically different; accordingly, the development of ligands is of pivotal importance to the field. So far, iron complexes with tetradentate nitrogen (N4, generally aminopyridine) ligands have shown to be most successful in achieving highly regio- and stereoselective oxidation reactions utilizing H2O2 as the oxidant. Amongst them, iron complexes with a cis-α topology derived from linear bis-alkylamine-bispyridine (N2Py2) ligands have been proven to be most effective so far. This thesis describes several ligand modifications of the N2Py2 ligand platform, with the aim of either improving C–H oxidation selectivities or enhancing the lifetimes of Fe(N2Py2) complexes in oxidation catalysis. Furthermore, the practical use of the Fe(N2Py2) and Mn(N2Py2) complexes in the oxidation of a number of biologically or industrially relevant compounds, like steroidal derivatives, unsaturated fatty acids and their esters, and vegetable oils, is also investigated in this thesis.