As already shown in Scheme 1, for the one-pot deprotection of PtBAMA neat TFA is used at 50 °C to obtain [PEGx-b-PDhay]4. Figure shows the quantitative deprotection of the ester group and additionally the deprotection of >95% of the boc group after 10 h reaction time. The signal of the ester group is overlapping with the PEG backbone when CDCl3 is used as NMR-solvent. However, after deprotection of the boc group the leftover ester signal shifts towards lower ppm when a mixture of D2O/NaOD is used, which allows determining the quantitative cleavage of the ester group. As the star-shaped block copolymers after deprotection show limited solubility in all solvents except DMSO and water, both were used as potential solvents for SEC measurements. Unfortunately, in both cases either column interactions or noisy baselines prevented a meaningful evaluation of the obtained data. To assess the stability of the amide linkage between both blocks during the deprotection reaction we used 1 H-NMR spectroscopy. For that, the larger [PEG55-amide-Br]4 macroinitiator was stirred in a large excess of neat TFA at 50 °C for 10 h and, after workup, the ratio between PEG backbone and amide was compared, resulting in a cleavage of < 10% (Figure ). Additionally, all star-shaped block copolymers after deprotection showed signal for both segments in NMR spectroscopy.