To reproduce:

1. Add a RadRibbonBar with a RadDropDownListElement and some other elements.
2. Use the following code:

for (int i = 0; i < 5; i++)
{
    RadListDataItem item = new RadListDataItem();
    item.Text = "Item" + i;
    this.radDropDownListElement1.Items.Add(item);
}
this.radRibbonBar1.EnableKeyMap = true;
this.radDropDownListElement1.KeyTip = "S";         
this.radDropDownListElement1.DropDownStyle = Telerik.WinControls.RadDropDownStyle.DropDownList; 
3. Press Alt, then 2. You will see the key tips for the drop down and its sibling items. 
4. Press S. You are expected to be navigated to the RadDropDownListElement, but are not. 

Here it is illustrated the behavior: http://screencast.com/t/Qmvqufznjt