Ducati-Pramac rider Martin clocked 1min 30.388sec, with Italy’s two-time defending world champion Francesco Bagnaia second best 0.145sec behind on a Ducati.
Spanish teenager Pedro Acosta, 19, was third quickest on a GasGas Tech3 following by compatriot Maverick Vinales (Aprilia) and Italian Fabio Di Giannantonio (Ducati-VR46).
Six-time world champion Marquez fell at the start of the session with the Spaniard unable to find his rhythm aboard his Ducati-Gresini.
The 31-year-old finished in 13th position and will have to go through Q1 on Saturday to join the 10 already through to Q2.
The top-10 riders participate directly in Saturday’s second qualifying session (Q2) to determine the starting grid for the sprint later in the day and Sunday’s race.
“This is the first Friday I’ve been in trouble,” Marquez said. “It happens, we now have to understand the reasons. Today, I fought against the bike.”
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