Alex Salmond said there was a "jobs gap in the No campaign's offer" of more powers if Scots reject independence in next month's referendum.
The SNP leader had challenged David Cameron to use his visit to Scotland this week to set out what additional powers to boost employment would be in line for if it stays in the UK.
He also pressed Better Together leader Alistair Darling on the issue when they went head to head in a BBC television debate.
The First Minister said that both Mr Cameron and Mr Darling had "confirmed the jobs gap in the No campaign's offer".
He said: "Scotland is one of the world's richest countries, wealthier per head than France, the UK and Japan.
"But despite our great wealth, almost everyone in Scotland will know of friends and family who have had to leave to get a job or further their career.
"With less than three weeks to go more and more people are finding out about the opportunity of independence to control tax, employment, trade and other jobs powers to ensure we can make the most of our wealth and vast resources."
Mr Salmond added: "Independence isn't a magic wand but we'll be able to tailor economic policy to put job creation in Scotland first instead of a Westminster policy which has consistently favoured London.
"The Scottish Government has already set out a long-term jobs plan which shows what can be achieved with control of key economic levers.
"By contrast, the failure of the No campaign to guarantee a single jobs power is important new information in the campaign as we reach decision point as a country."