Asymmetric Michael Addition of Dimethyl Malonate to 2‐Cyclopenten‐1‐One Catalyzed by a Heterobimetallic Complex

Abstract This chapter presents the step by step procedure for asymmetric michael addition of dimethyl malonate to 2‐cyclopenten‐1‐one catalyzed by a heterobimetallic complex. Heterobimetallic complexes have been developed to mimic catalytic activity found in biological enzymes. The heterobimetallic framework allows catalyst complexes to act as both a Lewis acid and a Brønsted base, while the ligand framework orients sites of reactivity in close proximity to one another. The chapter focuses on the synthesis of Shibasaki's Ga‐Na‐BINOL complex on large scale, and its use as a catalyst for the asymmetric Michael addition of dimethyl malonate to 2‐cyclopenten‐1‐one. Asymmetric Michael reactions of stabilized nucleophiles with Michael acceptors provide reliable access to chiral building blocks, often with high enantioselectivity. The chapter demonstrates the utility of Ga‐Na‐BINOL complex in the synthesis of Michael adduct in 90% yield and 99% ee on 31 g scale.