In Dropdown selection index changed event, remove the selected item from the dropdown.
It would be something like this,
GridViewRow grdrow = ((DropDownList)sender).Parent.Parent as GridViewRow;
DropDownList ddlProducts = (DropDownList)grd.Rows[grdrow.RowIndex].FindControl("YourDrpDown");
ddlProducts.Items.Remove(ddlProducts.SelectedItem);