If you're self-employed,* you can deduct 100% of your health insurance premiums as an above-the-line deduction. Whether you itemize or not, "above-the-line" deductions are subtracted from gross income to arrive at your AGI. This deduction cannot exceed the amount of income you have earned from your business.
* Sole proprietors are self-employed. Partners in partnerships, members of limited liability companies (LLCs), and certain employee/shareholders in S corporations may also be considered self-employed.