A couple of balls later, the left-arm spinner squared up Ajinkya Rahane, the ball took the outside edge of the bat and Peter Handscomb took an absolute blinder at second slip to leave India in dire straits at 95 for 5.
Australia then found the first wicket when Josh Hazlewood in his first over had Vijay (10) caught behind.
Captain Steve Smith was unbeaten after a chance-filled 59, during which he was dropped three times, with all-rounder Mitchell Marsh 21 not out.
With a new batsman at the crease, skipper Steve Smith re-introduced Starc with immediate effect.
After the breakthrough, India's bowlers went in for the kill in the second session.
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Shadow employment minister Brendan O'Connor has told Sky News Labor will be calling on the parliament to remidy this decision. The issue is likely to dominate next week's parliamentary question time and Senate estimates hearings on workplace relations.
Australia paceman Mitchell Starc has raised his game to the next level and India's batsmen need to be wary of his ability to trouble them with reverse swing, home captain Virat Kohli said on the eve of the first Test beginning on Thursday. Rahul completed a valiant half century and the pair added 50 runs for the 4th wicket and it was seeming that India have shrugged off the early blows and now they are ready to elongate their good work, but then the mega collapse arrived.
Handscomb was caught right in front of the wicket by Jadeja with a quicker, straight ball and five balls later Ashwin had Smith caught at mid-wicket coming down the track in a rush of blood. At 32, he knew this tour was make or break for his worldwide career, after the disappointment of being forced home from Sri Lanka, which had been followed by a drunken incident at a Sydney hotel that led to a fine from Cricket Australia.
Steven Smith won the toss and had no doubt whatsoever to bat first on a pitch that had turn from ball one. His dismissal was swiftly followed by the departure of Steve O'Keefe and Nathan Lyon who both fell for ducks off consecutive Umesh deliveries. Umesh Yadav became his sixth victim with India being bundled out inside 42 overs.
Starc dismissed Pujara with a rising delivery that brushed the batsman's glove and sailed through to wicketkeeper Matthew Wade.
India are unbeaten in 19 tests over a 18-month period with South Africa, New Zealand, England and Bangladesh all vanquished at home, while trips to Sri Lanka and West Indies also culminated in victories. It took O'Keefe no more than 23 balls in the post-lunch session to claim all his six wickets as India were all out for 105. He scored at least one boundary against all the bowlers with O'Keefe being hit for a six.
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