The flexibility provided by Distributed Energy Resources (DER) and Demand Response (DR) can enhance the ability of distribution networks to accommodate renewable generation and new high-peak/coincident loads. However, flexibility is not infinite, and its use in providing local services to distribution system operators (DSOs) can limit its availability for system ancillary services, required by transmission system operators (TSOs) to ensure security and adequacy. As the energy transition progresses, competition for flexibility between TSOs and DSOs will increase. Similar interaction appears between Medium Voltage (MV) and Low Voltage (LV) grids, for instance, when smaller DSOs are supplied by MV distribution networks operated by a different DSO. The Secondary Substation (SS), the interface between the MV and the LV, can provide ancillary services by changing its working point to keep the MV network operation within technical boundaries. Forecasting the SS behaviour is challenging due to the limited observability of LV networks and the uncertainty of generation/consumption patterns. This paper proposes a methodology that identifies and forecasts the amount of flexibility LV can offer without compromising its operation. To address data scarcity, a suitable methodology for developing and using synthetic networks is also proposed. Case studies demonstrate the validity of the proposed approach.