Described is the asymmetric synthesis of the allylic alcohols 11 (85% ee), 15 (99% ee), 17 (93% ee), 19 (61% ee), and 21 (69% ee) through a Pd-catalyzed reaction of the unsymmetrical carbonates rac- 10 , rac- 12 , rac- 14 , rac- 16 , rac- 18 , and rac- 20 , respectively, with KHCO 3 and H 2O in the presence of bisphosphane 6 . Similarly the allylic alcohols 23 (99% ee) and 25 (97% ee) have been obtained from the symmetrical carbonates rac- 22 and rac- 24 , respectively. Reaction of the meso-biscarbonate 26 with H 2O and Pd(0)/ 6 afforded alcohol 27 (96% ee), which was converted to the PG building block 32 . The unsaturated bisphosphane 33 showed in the synthesis of alcohols 36 , 37 , and 39 a similar high selectivity as 6 . The formation of alcohols 11 , 15 , and 17 involves an efficient dynamic kinetic resolution.