Catalysis by defined transition-metal complexes has captivated the attention of the scientific community over the last decades. The well-documented utility of Rh(III) complexes in C−H activation reactions have enabled the development of a plethora of new catalytic methods. High-valent transition-metal species in C−H activation reactions were first predicted in palladium-based transformations. From those early studies, it was apparent that differences in reactivity and selectivity could be expected. By analogy, higher valent Rh(V) complexes could represent a new approach in C−H activation reactions and offer different opportunities to improve and broaden the current state-of-the-art in the field.

A spiroketal bisphosphine (SKP) derived chiral digold complex is identified as a powerful catalyst for the highly diastereo- and enantioselective synthesis of spirocyclopropyloxindoles from diazooxindoles and a broad range of alkenes, including both cis and trans 1,2-disubstituted alkenes.

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The first Cp*Rh(III) -catalyzed arylation of unactivated C(sp(3) )-H bonds is presented. The unactivated primary C(sp(3) )-H bond of 2-alkylpyridines can be activated by Rh(III) and further reacts with triarylboroxines to efficiently build new C(sp(3) )-aryl bonds. The methodology also provides a facile and efficient synthesis of unsymmetrical triarylmethanes by Rh(III) -catalyzed C(sp(3) )-H arylation of diarylmethanes.