Mr Madders, a Shadow Health Minister, asked whether an offer had been rejected by the Health Secretary despite it being backed by those negotiating on his behalf.
Doctors at the Countess of Chester Hospital and across the country will stage a 24-hour walkout over contracts on Wednesday.
Mr Madders said: "Let me ask the Health Secretary a very direct question.
"Has the government at any point rejected a cost-neutral proposal from the BMA on the junior doctor contract?
"Yes or no?"
The Health Secretary shook his head - but would not give a one-word answer.
Watch: Video from our sister paper the Mirror of Justin Madders posing question to Jeremy Hunt
Instead he told MPs: "The only reason we do not have a solution on the junior doctors is because in December on the one outstanding issue, which is about pay on Saturdays, the BMA said they would negotiate, but last month they said they refused to negotiate.
"That's the only outstanding issue. If they're prepared to negotiate and be flexible on that, so are we."
A source from the British Medical Association, the union representing junior doctors, claimed Mr Hunt had vetoed an offer which dealt with the final sticking point of weekend pay.
The BMA source told the Independent : "The one person who would not agree was Jeremy Hunt. Even though the NHS Employers and Department of Health teams thought this was a solution he said no."
Emergency and urgent care, such as A&E, will not be affected by tomorrow's industrial action, the second walkout in a month.
But NHS chiefs say 2,884 operations have already been cancelled for the day of the strike.
It is thought the alleged deal could have been offered by the BMA some time before the new year.
NHS Employers chief executive Danny Mortimer said the BMA had offered no "substantive proposals" since 2016 began.
Asked to respond to the claims from the BMA source, a Department of Health spokesman said: "This is completely untrue.
"The BMA has continuously refused to discuss unsocial hours pay, despite their agreement to talk about this as part of ACAS in November and the progress we've made on safety, education and training."
The BMA declined to comment.
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