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The unique electronic and steric parameters of chiral cyclic alkyl amino carbene (CAAC) ligands render them appealing steering ligands for enantioselective transition-metal catalyzed transformations. Due to the lack of efficient synthetic strategies to access particularly attractive α-chiral CAACs assessment and exploitation of their full synthetic potential remain difficult. Herein, we report a streamlined strategy to assemble a library of diastereo- and enantiomerically pure CAAC ligands featuring the notoriously difficult to access α-quaternary stereogenic centers. A tailored Julia-Kocienski olefination reagent allows the Claisen-rearrangement to be leveraged as an expedient route to form the synthetically pivotal racemic α-chiral methallyl aldehydes. Subsequent condensation with chiral amines and further cyclization provided a library of diastereomeric mixtures of the targeted ligand precursors. The CAAC salts as well as their corresponding metal complexes are conveniently separable by standard silica gel flash chromatography closing a long-standing accessibility gap in chiral CAAC ligands with proximal α-chirality. The rapid availability of both diastereomers enables testing of the relevance and synergistic effects of two chiral centers on the ligand in catalytic applications. A broad range of metal complexes with copper, gold, rhodium and ruthenium were obtained and structurally analyzed. The catalytic performances of the corresponding chiral CAAC copper and ruthenium complexes were assessed in enantioselective conjugate borylations and asymmetric ring closing metathesis, displaying selectivities of up 95 : 5 er., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The 1,1,2,2-tetrafluoroethylene unit is prevalent in bioactive molecules and functional materials. Despite being in principle a straightforward strategy to access this motif, the direct tetrafluorination of alkynes involves very hazardous or inconvenient reagents. Therefore, safer and convenient alternatives are sought after. We developed a mild and operationally simple perfluorination method converting 1-alkynyl triazenes into 1,1,2,2-tetrafluoro alkyl triazenes, employing cheap and readily accessible reagents. Moreover, a judicious tuning of the reaction conditions enables access to α-difluoro triazenyl ketones. Complementary, electrophilic fluorination of alkynyl triazenes gives rise to the regioisomeric α-difluoro acyl triazenes. These three chemo- and regio-divergent protocols enable access to elusive fluorinated 1-alkyl and 1-acyl triazenes, thus expanding the chemical space for these unusual entities. Furthermore, several reaction intermediates and side products revealed insights on the reaction pathways that may be useful for further fluorination chemistry of alkynes., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

The 2-pyrone motif occurs frequently in bioactive natural products and is appreciated as synthetic intermediates. However, only few methods allow for diversifying functional group modifications on this relevant heterocycle. The distinct properties of 1-alkynyl triazenes promote a smooth addition of propiolic acids across the triple bond. Addition of catalytic amounts of silver salt induces cyclization to 2-pyrones. Depending on the reaction temperature, either 6-triazenyl or 5-triazenyl 2-pyrones are selectively formed. The triazenyl unit is subsequently replaced by a variety of valuable groups in a one-pot process yielding for instance 2-fluoro pyrones. The substitution occurs with an intriguing 1,5-carbonyl transposition. Moreover, the triazenyl group serves as traceless activating group for subsequent Diels-Alder cycloadditions and as a constituting unit for rare fused aminopyrazole pyrone heterocycles., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Chiral cyclopentadienyl Rh III complexes efficiently catalyze enantioselective cyclopropanations of electron-deficient olefins with N -enoxysuccinimides as the C1 unit. Excellent asymmetric inductions and high diastereoselectivities can be obtained for a wide range of substrate combinations. The reaction proceeds under mild conditions without precautions to exclude air and water. Moreover, the synthetic utility of the developed method is demonstrated by concise syntheses of members of the oxylipin natural products family and the KMO inhibitor UPF-648.

A trisubstituted chiral Cp x ligand family is introduced. Based on the disubstituted atropchiral Cp x ligand scaffold, the introduction of a bulky third substituent at the central position of the Cp ring leads to substantially increased selectivities for rhodium(iii)-catalyzed kinetic resolutions and allowed for s -factors of up to 50. Their superiority is demonstrated by kinetic resolutions of phosphinic amides providing access to compounds with stereogenic phosphorus(v) atoms. The unreacted acyclic phosphinic amide and the cyclized product are both obtained in good yields and enantioselectivities. The ligand synthesis capitalizes on a late stage modification and expands the accessible ligand Cp x ligand portfolio.