The 2021 F3 runner-up set a 1m40.542s to top the timesheet for only his third F2 feature race, after contesting the final two F2 rounds of 2021 for MP Motorsport.
Doohan, who joined the Alpine Academy during the off-season, pipped ART Grand Prix driver Pourchaire to the top spot by just over a tenth of a second in a session that was red flagged after just 58 seconds.
DAMS rookie Ayumu Iwasa span off at Turn 2 on his first lap out of the pits, the Japanese beaching his car in the gravel and ruining his qualifying as a result.
The Van Amersfoort Racing pair were first out on track when action resumed five minutes later, with Jake Hughes setting the first fast lap of the session with a 1m41.469s.
Doohan went straight into second with his first flying lap, setting a 1m41.614s, less than two-tenths behind Hughes.
Felipe Drugovich (MP Motorsport) briefly knocked Hughes off the top of the leaderboard, setting a 1m41.210s, before the Briton recaptured the top spot with a 1m41.121s.
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