TY - BOOK AU - Peeters,J. AU - Palmans,A.R.A. AU - Veld,M. AU - Scheijen,F. AU - Heise,A. AU - Meijer,E.W. TI - Cascade Synthesis of Chiral Block Copolymers Combining Lipase Catalyzed Ring Opening Polymerization and Atom Transfer Radical Polymerization N2 - The enantioselective polymerization of methyl-substituted ¤-caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl-¤-caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the enantiopreference of differently substituted monomers was observed. The combination of 4-methyl-¤-caprolactone with Novozym 435 showed good enantioselectivity also in bulk polymerization and resulted in enantiomerically enriched P((S)-4-MeCL)(eep up to 0.88). Subsequently, a novel initiator combining a primary alcohol to initiate the ring opening polymerization and a tertiary bromide to initiate atom transfer controlled radical polymerization (ATRP)was synthesized, and showed high initiator efficiencies (>90 UR - https://drive.google.com/file/d/1tNQPiM9eqtRr2OF0imCckDaFmiJDCNr4/view?usp=drivesdk ER -