Courtesy De Kock's 102-ball-113 that had 13 boundaries and three huge sixes, South Africa 'A' scored a massive 542 in their first essay.
At stumps, India 'A' were in a spot of bother finishing the day at 122 for three with their openers Jiwanjot Singh (22), Abhinav Mukund (38) and No. 3 batsman Shreyas Iyer (49) getting out after being set well.
South African team management's decision to send De Kock to India before the senior team's visit is turning out to be a masterstroke as the stylish left-handed wicketkeeper-batsman has made full use of the opportunities.
He has scored two centuries in the tri-series of 'A' teams and now scored another attacking hundred as he flayed the Indian bowling.
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While Axar Patel (4/115) turned out with best figures, his bowling neither had variation nor the sting to trouble De Kock or skipper Dane Vilas (75) who also helped himself with 10 fours and two sixes.
When Indians batted, Jiwanjot and Mukund negotiated the first hour, adding 43 runs before off-spinner Dane Piedt got his team the first breakthrough. He bowled Jiwanjot with a turning delivery as the Punjab opener's 22 off 39 balls had three fours.
Mukund, who hit some attractive shots on both sides of the wicket struck a nice partnership with Iyer as they added 45 runs for the second wicket.
Young Munbai batsman Iyer, who looked in fine form as he struck 10 boundaries in his 49 off 61 balls, was bowled when a Wayne Parnell delivery held its line to castle him.
At stumps, Karun Nair (0) and skipper Ambati Rayudu (11) were at the crease.