The main focus of this thesis lies in the development of new transition metal-catalyzed chemoenzymatic dynamic kinetic resolutions (DKR) of both alcohols and amines. The first part of the thesis deals with the development of new heterogeneous systems for the DKR of amines. The racemization catalysts in these different systems are all composed of palladium nanoparticles supported on either mesoporous silica or incorporated in a biocomposite that is composed of a bioactive cross-linked enzyme aggregate. 

The second part of the thesis deals with the development of a homogeneous iron catalyst in the racemization of sec-alcohols for the implementation in a chemoenzymatic DKR. Two protocols for the racemization of sec-alcohols are reported. The first one could not be combined with a chemoenzymatic kinetic resolution, although this was overcome in the second iron based protocol. 

Following the successful iron catalyzed chemoenzymatic DKR of sec-alcohols, the iron catalyst was used in the cyclization of α-allenic alcohols and N-protected amines to furnish 2,3-dihydrofurans and 2,3-dihydropyrroles, respectively. The cyclization is proceeding in a diastereoselective manner.

The last part of the thesis deals with attempts to further elucidate the mechanism of activation of a known ruthenium racemization catalyst. X-ray absorption spectroscopy using synchrotron radiation was used for this purpose.

The focus of this thesis is twofold: The first is on the application of iron catalysis for organic transformations. The second is on the use of in situ X-ray absorption spectroscopy (XAS) to investigate the mechanisms of a heterogeneous palladium-catalyzed reaction and a homogeneous ruthenium-catalyzed reaction.

In chapters two, three and four, the use of iron catalyst VI, or its analog X, is described for (I) the DKR of sec-alcohols to produce enantiomerically pure acetates; (II) the cycloisomerization of α-allenols and α-allenic sulfonamides, giving 2,3-dihydrofuran or 2,3-dihydropyrrole products, respectively, with excellent diastereoselectivity; and (III) the aerobic biomimetic oxidation of primary- and secondary alcohols to their respective aldehydes or ketones.

In the fifth chapter, XAS is used to elucidate the mechanisms of a Pd(II)-AmP-MCF-catalyzed lactonization reaction of acetylenic acids. The catalyst was known to deactivate during the reaction and the XAS studies identified the cause of this deactivation. A reactivation strategy was subsequently developed based on these findings.

In the sixth and final chapter, XAS is used to examine the activation mechanism of a ruthenium racemization catalyst and a ruthenium-acyl intermediate which had previously been speculated to be formed in the activation process was confirmed.