Homogeneous Two-Component Polycondensation without Strict Stoichiometric Balance via the Tsuji−Trost Reaction:  Remote Control of Two Reaction Sites by Catalysis

Carothers and Flory established the fundamental principles of homogeneous two-component polycondensation reactions by which a variety of commonly used polymers such as polyesters and polyamides (nylons) are synthesized even now. One of the most critical factors to achieve a high degree of polymerization is a strict adherence of stoichiometric balance of the two components. An imbalanced ratio of the two starting materials leads to lower degree of polymerization and, consequently, polymers of poor quality. Here we report the details of a strategy, validated by appropriate experiments, which enables an efficient homogeneous two-component polycondensation via palladium-catalyzed allylic substitution (the Tsuji−Trost) reaction without strict stoichiometric balance.