Putin was not included on a list of Moscow's negotiating team published by the Kremlin late on Wednesday, after Zelensky challenged him to turn up in person to the talks.
But the absence of Putin -- as well as any top diplomats such as Foreign Minister Sergei Lavrov or foreign policy aide Yuri Ushakov -- would seem to diminish the talks' importance or any possibility of a breakthrough.
Russia now occupies about a fifth of Ukraine's territory.
A Ukrainian official told AFP that Zelensky was en route to Ankara, where he will meet Turkish President Recep Tayyip Erdogan, and only then would decide his approach to the talks.
Hundreds of journalists were gathered at the Dolmabahce Palace in Istanbul, where the talks are rumoured to be taking place, AFP reporters saw.
Trump has been pushing for a swift end to the three-year war but has become frustrated with a lack of progress and has encouraged the two sides to open direct talks.
Speaking at a NATO meeting in Antalya, US Secretary of State Marco Rubio said Washington was “impatient” for progress and willing to consider “any mechanism” to achieve a lasting end to the war.
Zelensky had spent days urging Putin to turn up after the Russian leader himself proposed direct Russia-Ukraine talks at the weekend.
“This is his war... Therefore the negotiations should be with him,“ Zelensky said in one statement.
'Cautiously optimistic'
Medinsky, born in Soviet Ukraine, led the failed 2022 negotiations in which Moscow called for sweeping territorial claims and restrictions on Kyiv's military.
Russia's other three negotiators were named as Deputy Foreign Minister Mikhail Galuzin, Deputy Defence Minister Alexander Fomin and Igor Kostyukov, director of Russia's GRU military intelligence agency.
Putin held a briefing with his negotiating team and Russia's top foreign policy and defence officials in Moscow on Wednesday before they departed for Istanbul, the Kremlin said.
Russia insists the talks address what it calls the “root causes” of the conflict, including a “denazification” and demilitarisation of Ukraine.
It has also repeated that Ukraine must cede territory occupied by Russian troops and pull out of some areas still under Ukrainian control.
But Zelensky has acknowledged that Ukraine might only get them back through diplomatic means.
If the Russians “play ball... you could get to some breakthroughs over the next couple of weeks”, he said.
European leaders have said new sanctions will be quickly imposed on Russia if the Istanbul talks do not produce results.
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