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C8H12CuN10O6, triclinic, P 1 ‾ (no. 2), a = 7.6063(5) Å, b = 9.3072(7) Å, c = 10.8485(8) Å, α = 81.370(2)°, β = 75.503(2)°, γ = 84.756(2)°, V = 733.97(9) Å3, Z = 2, Rgt(F) = 0.0515, wRref(F2) = 0.1194, T = 120(2) K. [ABSTRACT FROM AUTHOR]

The reactions of the gold(I) metalloligand [Au2{μ(P,C)-Ph2Pfc}2], where fc stands for ferrocene-1,1′-diyl, with bare or ligand-stabilised group 11 metal ions open access to diverse oligometallic clusters stabilised by Au–Au, Au–Ag and Au–Cu interactions. These capping reactions and the unique structures of the products stem from unparalleled properties of the bridging ferrocene groups, namely their structural flexibility and electron-rich nature, which enable accommodating the capping moieties and supporting ligands and facilitate electrophilic metalation, respectively. While the Au+ and Ag+ ions behave similarly, capping reactions with Cu+ proceed differently, with an accentuated role of the counter ions and other ligands in the system. Such behaviour reflects the relative strengths of the Au–M metallophilic interaction (M = Au, Ag and Cu), among which the Au–Cu interactions are the weakest, as confirmed by DFT calculations. [ABSTRACT FROM AUTHOR]

The synthesis of enantiopure chiral boron dipyrromethenes (BODIPYs) is of importance due the intrinsic properties of BODIPYs as fluorophores that could be used as probes for molecular sensing. The present study reports an asymmetric organocatalytic cascade reaction of meso‐chloromethyl BODIPY derivatives with α,β‐unsaturated aldehydes catalyzed by a chiral secondary amine. The corresponding BODIPY‐derived cyclopropanes were produced in isolated yields 66–98%, and with diastereomeric ratios 3/2–>20/1, and 92–99% ee for major diastereomer. The synthetic utility of the protocol was exemplified on a set of additional transformations of the corresponding optically pure compounds. In addition, a study explaining the reaction mechanism (DFT computations) and photophysical characterization of all enantioenriched products were accomplished. [ABSTRACT FROM AUTHOR]

Pentasubstituted pyrrolidines are ubiquitous constituents of natural products and drugs, however the access options to them especially with respect to absolute and relative stereochemistry are not well developed. We report an asymmetric synthesis of N,2,3,4,5‐pentasubstituted pyrrolidines by oxidative single‐electron transfer‐catalyzed tandem aza‐Michael addition/radical 5‐exo cyclization/oxygenation reactions. The absolute stereochemistry is set by applying readily accessible chiral allylamines in asymmetric conjugate additions to various β‐substituted‐α,β‐unsaturated esters, which dependent on the substituent R2 sets the configuration of the two stereocenters next to the amine function, whereas two more are diastereoselectively generated by the radical 5‐exo cyclization step. This allows the diastereodivergent single‐step synthesis of pyrrolidines with four contiguous stereogenic centers. The stereoselectivity is rationalized by a predictive model. [ABSTRACT FROM AUTHOR]