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Bernardo Tolomei, founder of the Olivetan Benedictine Order, and the abbey of Monte Oliveto Maggiore, in the municipality of Asciano, also founded the monastery of Sant'Anna in Camprena, in 1324, along the road that links Castelmuzio to Pienza. The name “Camprena” appears to derive from the sandy nature of the soil (campus arenae). It was abandoned in the eighteenth century and in 1970 restoration was started to transform it into the prestigious relais, owned by the diocese.