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Hiking in Tuscany

I was reading about hiking the 'white roads' in Tuscany, and was perusing the map for possible pairs of towns for which taking the bus from Siena to one town, hiking to the other, and taking the bus back to Siena, might work. If it's not more than 5-6 miles, I think I'm game. So far, I've come up with Pienza and Montepulciano. Any thoughts, warnings, cheers, jeers? Any other ideas for pairs of towns?