Nadal's path to a possible sixth Madrid title was cleared of second seeded Daniil Medvedev and fourth-seeded Monte Carlo champion Stefanos Tsitsipas who were both shock third round losers.
Argentina Open: Sumit Nagal stuns World No 22 Cristian Garin in straight sets to enter quarter-finals
Nagal, ranked 150, produced high-class tennis on Wednesday to register an impressive 6-4 6-3 second round win over his Chilean rival
Garin, ranked 22nd, and top-ranked American John Isner, 25th overall, lead a 28-player field at the start of a revamped schedule that will not return to US soil until the Miami Open in March.
Isner, 35, owns 15 ATP titles, including 13 on US soil, but has never lifted the trophy at Delray Beach.
Top-seeded Djokovic lost four straight games and had to save a set point before beating Filip Krajinovic 7-6 (6), 6-3 in an all-Serbian match, and No. 2 Thiem nearly squandered a 5-1 lead in his 6-4, 7-5 win over Vitaliy Sachko of Ukraine.
Bopanna and Shapovalov had defeated the pair of Argentina's Guido Pella and Chile's Cristian Garin 6-4, 6-4 to qualify for the round of 16.
Australian Open 2020: Roger Federer cruises into third round; Fabio Fognini emerges victorious after marathon five-setter
Checkout all the match results of the men's singles fixtures from the third day of the Australian Open 2020.
ATP Cup 2020: Former US Open champion Marin Cilic powers Croatia to victory over Poland; Japan ease past Georgia
Cilic, who has a career-high ranking of No 3 but slipped to 38 after an injury-shortened 2019 season, has now won both his singles matches for Croatia in Sydney at the new international men's team event
Monfils said he was motivated because he didn't want to let down Gilles Simon, who is nominated as a player-captain for France.
Rafael Nadal and Novak Djokovic, fighting it out for the year-end world number one spot, edged closer to a possible Paris Masters final clash as both eased into the last four on Friday
Paris Masters 2019: Daniil Medvedev says he is preparing for 'dream' debut at ATP finals after shock second-round defeat to Jeremy Chardy
Medvedev will next head to London for his maiden appearance at the ATP Tour Finals next month, where he is hoping to emulate last year's champion and fellow youngster Alexander Zverev
ATP Paris Masters 2019: Daniil Medvedev suffers first defeat since US Open final; defending champion Karen Khachanov bundled out
Medvedev, who had reached six successive finals, looked in control when he took the first set but he ultimately paid for failing to convert 14 of the 15 break points he carved out
Munich Open: Cristian Garin's remarkable breakthrough continues as Chilean beats Matteo Berrettini to win second ATP title
Chilean Cristian Garin continued his remarkable breakthrough season as he defeated Matteo Berrettini 6-1 3-6 7-6(1) in the Munich Open final on Sunday, clinching his second ATP title.
Munich Open: Cristian Garin upsets third seed Marco Cecchinato in straight sets to reach his third ATP final of season
Chile’s Cristian Garin upset third seed Marco Cecchinato 6-2, 6-4 to reach his third ATP final of the season at the Munich Open on Saturday.
Munich Open: Alexander Zverev says nothing is going in his favour after shock quarter-final defeat to Cristian Garin
World No 3 Alexander Zverev complained that everything was against him after a shock defeat in the quarter-finals of the Munich Open on Friday.