The application of C1‐symmetrical diphosphite ligands containing furanose backbone in the Rh‐catalysed asymmetric hydroformylation of norbornene is described. The catalysts were highly active and produced exclusively exo‐norbornanecarboxaldehyde with enantioselectivities (ee) up to 71 %. Considering these promising results, the ligands were modified with a pyrene moiety to accomplish their immobilisation onto carbon materials. The corresponding Rh complexes bearing the novel pyrene‐tagged ligands were synthesised and immobilised onto multiwalled carbon nanotubes (MWCNT), reduced graphene oxide (rGO) and carbon beads (CBs). The novel catalytic systems were tested in the asymmetric hydroformylation of norbornene providing similar performance in terms of both activity and selectivity compared to the non‐immobilised systems. The recyclability of the new heterogenised catalysts was studied in the target reaction in batch mode. Nevertheless, the recycling was unsuccessful due to catalyst leaching. When used under continuous flow mode, these catalysts revealed robust and provided even higher ee than the corresponding homogeneous systems.

The first successful rhodium catalysed asymmetric hydroaminomethylation of alkenes using a single catalyst is reported with ees up to 86%.

The successful rhodium-catalyzed asymmetric hydroformylation and hydroaminomethylation of α-substituted acrylamides is described using 1,3-phosphite-phosphoramidite ligands based on a sugar backbone. A broad scope of chiral aldehydes and amines were afforded in high yields and excellent enantioselectivities (up to 99%). Furthermore, the synthetic potential of this method is demonstrated by the single-step synthesis of the brain imaging molecule RWAY.

The synthesis of β 2,2 -amino esters was successfully achieved via Rh-catalysed regioselective hydroaminomethylation of methyl methacrylate with secondary amines using the neutral precursor [Rh(acac)(CO) 2 ]. In this process, the presence of molecular sieves revealed crucial in order to access the final amino ester. For the synthesis of products containing aniline derivatives, the use of the cationic precursor [Rh(COD) 2 ]BF 4 and Me CgPPh phosphine as ligand was necessary in a mixture of toluene/ DCE as solvent. Effects of the steric and electronic properties of the amines were observed during this study. Interestingly, poisoning effect of CO in the hydrogenation of the imine intermediate was observed when benzyl amine was used.

Ametal-free C À Hallylation strategy is described to access diverse functionalized ortho-allyl-iodoarenes.T he method employs hypervalent (diacetoxy)iodoarenes and proceeds through the iodane-guided "iodonio-Claisen" allyl transfer.T he use of allylsilanes bearing electron-withdrawing functional groups unlocks the functionalization of ab road range of substrates,i ncluding electron-neutral and electronpoor rings.T he resulting ortho-allylated iodoarenes are versatile building blocks,w ith examples of downstream transformation including ac oncise synthesis of the experimental antimitotic core of Dosabulin. DFT calculations shed additional light on the reaction mechanism, with notable aspects including the aromatic character of the transition-state structure for the [3,3] sigmatropic rearrangement, as well as the highly stereoconvergent nature of the trans-product formation.

A stepwise build-up of multi-substituted Csp3 carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how gem-α,α-dimetalloid-substituted benzylic reagents...

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Ametal-free C À Hallylation strategy is described to access diverse functionalized ortho-allyl-iodoarenes.T he method employs hypervalent (diacetoxy)iodoarenes and proceeds through the iodane-guided "iodonio-Claisen" allyl transfer.T he use of allylsilanes bearing electron-withdrawing functional groups unlocks the functionalization of ab road range of substrates,i ncluding electron-neutral and electronpoor rings.T he resulting ortho-allylated iodoarenes are versatile building blocks,w ith examples of downstream transformation including ac oncise synthesis of the experimental antimitotic core of Dosabulin. DFT calculations shed additional light on the reaction mechanism, with notable aspects including the aromatic character of the transition-state structure for the [3,3] sigmatropic rearrangement, as well as the highly stereoconvergent nature of the trans-product formation.