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If Djokovic sees off Struff, he could be destined for a third-round meeting with British No. 1 Dan Evans, who is seeded for the first time at a Grand Slam in Melbourne and has been drawn to face world No. 132 Mackenzie McDonald in the first round.
Evans lost overnight to up-and-coming Russian Andrey Bublev in ATP Adelaide, 6-4 3-6 6-3.
Federer, chasing a 21st Slam, is unlikely to be tested until the fourth round, with the Swiss maestro meeting American Steve Johnson in his opener.
However, Denis Shapovalov or Grigor Dimitrov potentially await him at the start of the second week.
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If the seeds progress as expected, Djokovic, searching for an eighth Australian Open title, will face 20-time Grand Slam winner Federer in the semi-finals. Djokovic won all eight matches when inspiring Serbia to victory in the recent ATP Cup.
Top seed Rafa Nadal should have no problems in his first-round match against Hugo Dellien, but a possible clash with home favourite Nick Kyrgios is looming in the fourth round.
Britain's Kyle Edmund, a shock semi-finalist in 2018, faces a tough first-round test against No. 24 seed Dusan Lajovic. Cameron Norrie, the British No. 3, takes on Pierre-Hugues Herbert.