The First Minister dismissed concerns raised by the bosses of BP and Sainsbury's this week as coming from members of the "political elite".
He said the debate should focus on issues such as childcare and the so-called bedroom tax, telling his opponents: "Don't cite the elite, cite the people of Scotland."
Mr Salmond spoke out after a series of high-profile interventions by business leaders this week.
On Tuesday, BP chief executive Bob Dudley said there were "quite big uncertainties" over currency, EU membership and tax regimes if Scotland were to leave the UK.
The next day Sainsbury's chief executive Justin King warned the firm faced higher costs, sparking fears prices could rise under independence. His comments echoed concerns raised last year by Asda and Morrisons chiefs.
In response, Mr Salmond said there were "many, many chief executives" who supported independence.
Yesterday he was challenged by Scots Labour leader Johann Lamont to back up the claim.
During Holyrood exchanges she told him: "The chief executives of BP, Sainsbury's, Asda and Morrisons have all warned about the consequence of independence.
"The First Minister says 'there are many, many chief executives' who are in favour of his plan.
"Again, I ask him to name the 'many, many chief executives' of businesses that are comparable to BP and the supermarkets who actually back him."
He said: "Johann Lamont has talked about nothing else but the political elite in this question.
"Let's talk the language of people - let's talk about jobs, investment.
"Let's talk about the transformation of childcare, let's talk about the bedroom tax, let's talk about what this Parliament has achieved.
"Don't cite the elite, cite the people of Scotland."
Despite being asked three times, Mr Salmond declined to name a pro-independence company chief but said Business for Scotland, a campaign group linked to Yes Scotland, had a list of hundreds.
A spokesman for the First Minister said later: "There are chief executives of large, medium and small firms who back independence for Scotland.
"Bob Dudley's opinions are worth no more than anyone else's.
"There are huge profits to be made in the North Sea whether Scotland is independent or not."
Iain McMillan, director of the CBI in Scotland, warned: "If the people of Scotland vote Yes it will have profound and long lasting effects on Scotland's economy and business, especially businesses who have to trade across the Border and with the wider world."
At Westminster, a spat broke out over claims the UK Government was seeking to pressure firms to back the No campaign.
The SNP hit out after Philip Dunne, the Defence Procurement Minister, said he wanted to see Scottish defence firms expressing their concerns about independence "at every opportunity".
Westminster SNP leader Angus Robertson said it showed UK Government ministers were "attempting to pressure companies, which depend on MoD orders and contracts, to speak out on behalf of the No campaign".
However, David Mundell, the Scotland Office Minister, accused Mr Robertson of "panic" and, referring to business leaders who had come out this week against independence, said: "It is clear that when confronted with fair questions and uncomfortable truths the SNP is resorting to a bunker mentality."