Studies of the polymerization of racemic propylene sulfide (PS) by n-BuLi-(-)LiOR* (* denotes chiral group) show that the development of optical activity in the polymers can arise both by the ordinary asymmetric selective polymerization of (S)-PS and by two secondary reactions: first, by selective desulfurization of (R)-PS (both the unreacted PS and the polymer have a negative rotation at small conversions of PS into polymer); and second, by selective decomposition of (S) polymer chains. The latter is also confirmed by the asymmetric decomposition of optically inactive poly(propylene sulfides) by the same catalytic system. Possible reaction mechanisms for these processes are considered.

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