In order to study the click and release kinetics various allylic functionalized TCO derivatives were synthesized. First, we aimed to monitor the click and release reactions with F-NMR spectroscopy by eliminating a fluorinated payload upon tetrazine activation. The allylic alcohols of the TCOs 7, 8, 13 and 14 were functionalized with a pentafluorophenyl (PFP) group (Scheme 3). The exo-PFP derivatives were synthesized in one step from 7 and 8 with bis(pentafluorophenyl) carbonate (DPFPC) and N,N-diisopropylethylamine (DIPEA) in dichloromethane to afford 15 and 16 in 43 and 32% yield, respectively. Although the deacetylated endo-TCOs were obtained as a mixture of axial and equatorial diastereoisomers, we still studied the release capabilities. Therefore, the endo-PFP analogues 17 and 18 were synthesized in a similar fashion with DPFPC and DIPEA in an overall 33% yield obtained as an inseparable mixture of the axial and equatorial derivatives (ratio 1:2.5 respectively). Having the new allylic functionalized TCO derivatives in hand, we set out to investigate the click and release kinetics with F NMR spectroscopy (Scheme 4). The functionalized TCOs 15, 16, 17 and 18 were dissolved in CDCl3, a solution of 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ, 19) was added and a F NMR spectrum was recorded every 48 seconds. In case of the axial-TCO 15, we observed complete release of the PFP moiety within 20 minutes. Further investigation of the click and release reactions with 15 revealed that at -20 °C solely the click conjugate was observed and no release of PFP was obtained. Only after elevating the temperature to 10 °C, the PFP carbonate was released upon tautomerization from the conjugated product at such a rate that the intermediate tautomeric product could not be observed (see: