The exploration of the scalar sector of the Standard Model is at the core of current and future science programs at collider experiments, with increasing focus on the self-interaction of the Higgs boson. This important parameter of the Higgs sector can be measured in various channels, among the production of a Higgs boson associated with a top-quark pair,tthh. In this paper we study this channel and its potential to measure or constrain the self-coupling and possible new physics contributions at a future 100 TeV proton-proton collider. Analysing this highly complex final state adds to the sensitivity for enhanced self-coupling interactions, and we argue that a measurement of this process is a necessity to constrain blind directions in the multi-dimensional parameter space of well-motivated new physics scenarios. * Electronic address: shankha.banerjee@durham.ac.uk † Electronic address: frank.krauss@durham.ac.uk ‡ Electronic address: michael.spannowsky@durham.ac.uk 1 A fully leptonic tt even though much cleaner, suffers from a reduction in the total rate. A fully hadronic scenario, on the other hand, arXiv:1904.07886v2 [hep-ph]