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Cinque Terre to Siena

Hi, this June my wife and I will be spending 2 nights in Cinque Terre followed by 2 nights in Siena and then 2 nights in Rome. We will be renting a car in La Spezia and driving down to Siena, keeping the car to explore and then turning in before heading to Rome. I would love some thoughts on the following itinerary....

La Spezia > Greve Chianti > San Gimignano > Siena (Day 1)
Siena > Val d'Orcia > Siena (Day 2)

Can anyone recommend a good loop for Day 2? We would like to visit Multipulciano and are open to any other suggestions as we have heard that region is awesome!

Thanks in advance!