Enabling Directional Sequence‐Control via Step‐Growth Polymerization of Heterofunctionalized Precision Macromonomers

: The synthesis of periodic copolymers with a regularly recurring sequence in one direction along the polymeric backbone is presented, applying a step-growth polymerization of heterofunctionalized precision macromonomers derived from solid phase synthesis (SPS) via photoinduced thiol-ene coupling (TEC). Heterofunctional macromonomers with monomer sequence-control of the AB type present a terminal alkene and a terminal thiol group carrying a photolabile protecting group to avoid uncontrolled polymerization by self-initiation. As protecting group, 3,4-methylenebisoxy-6-nitrobenzyl is attached onto the thiol via its bromide derivative directly on solid support. The protected heterofunctionalized macromonomer is polymerized in a two-step procedure, first cleaving the photolabile group and subsequent polymerization of the macromonomer via TEC, giving a high molecular weight polymer with M¯n of 23.8 kDa corresponding to a X¯n of 10 with one directional sequence-control due to their consistent head-to-tail linkage.