As reported, L-selectride gave the opposite sense of induction in comparison to NaBH4. Accordingly, the desired (R,S)-configured sulfinamides 57 were produced and purified by column chromatography to obtain single diastereomers. The auxiliary could easily be cleaved under mildly acidic conditions, and the resulting ammonium chlorides 58 were Boc-protected and coupled with 4-methylthiazole, yielding the building blocks 60. The (S)-configuration at the benzylic position of an exemplary compound of type 59 was confirmed by X-ray crystallography and inspection of the Flack parameter using Bayesian statistics on Bijvoet differences (Figure ). Particular representatives of type 60 (Scheme 4) were designed to contain the stereogenic center as part of a fused cycloaliphatic ring. By applying the same enantioselective synthetic strategy, corresponding partially hydrogenated indenone (n = 1) or naphthalenone (n = 2) derivatives 55e-g were used as starting materials. The five-step route afforded the bicyclic building blocks 60e-g. Next, we decided to orthogonally assess the VHL-ligand interaction of eight selected compounds (26-33) in a direct binding assay using surface plasmon resonance (SPR) (Table ).