First Minister Nicola Sturgeon will now meet European Commission president Jean-Claude Juncker on her visit to Brussels to discuss Brexit.
Ms Sturgeon has arrived in Brussels and will also hold talks with EU Parliament president Martin Schulz and MEPs.
She said she was “determined” to protect Scotland’s interests in Europe.
The first minister had been hoping to talk to President of the European Council Donald Tusk but he said it was not appropriate at this time.
Talks with Mr Juncker had been expected in the coming weeks, but a meeting has now been scheduled for Wednesday evening.
Speaking ahead of the talks, SNP MEP Alyn Smith said there was a lot of “goodwill” towards Scotland in Brussels.
Mr Smith received a standing ovation at the European Parliament on Tuesday after urging his colleagues “do not let Scotland down” in the wake of the Brexit vote.
He told BBC Radio Scotland’s Good Morning Scotland programme: “The doors in Brussels are open and there is a willingness to speak to Scotland.”
He added: “We’ll do whatever we need to do to best safeguard Scotland’s best interests, but my job at the moment is to get as many doors open as possible and as many things as possible on the table.
“Brussels is good at finding solutions to complex questions where there is a political will and goodwill to do so, and hopefully I demonstrated yesterday that there is a lot of goodwill for Scotland right now.”
What might Nicola Sturgeon ask European leaders?
By the BBC’s Scotland editor Sarah Smith
Today Scotland’s first minister will focus on reminding the EU that Scotland voted to remain.
Scotland “did not let them down” as SNP MEP Alyn Smith put it yesterday.
And she will ask that Scotland be given special consideration in the Brexit negotiations.
But this trip is also about telling Europe that Scotland may soon be an independent country which wants to remain inside the EU or, if it has to, rejoin on the most favourable terms possible.
If there is to be another referendum on Scottish independence it is vital that Scotland is made to feel it will receive a warmer welcome in Europe than was on offer in 2014.
Nicola Sturgeon’s visit to Brussels comes the day after Holyrood debated the EU referendum outcome.
She told the chamber on Tuesday afternoon: “These times call for principles, purpose and clarity – in short, for leadership.
“This is why the vacuum that has developed at Westminster is so unacceptable.
“Politicians who proposed this referendum – no matter how bruised they feel by the result – have a duty now to step up and deal with the consequences of its outcome.”
Her commitment to “maintain a strong Scotland in Europe” won cross-party support.
However, both the Scottish Conservatives and the Scottish Liberal Democrats said the aftermath of the vote should not be used to launch a second Scottish independence referendum.