Palladium-Catalyzed Regio‑, Enantio‑, and Diastereoselective Asymmetric [3 + 2] Cycloaddition Reactions: Synthesis of Chiral Cyclopentyl Phosphonates

The
palladium-catalyzed unified approach using in situ-generated
Phospha-TMM species to synthesize a diverse array of chiral organophosphorus
containing carbo- and heterocyclic compounds in a highly regio-, diastereo-
(>20:1 dr), and enantioselective (>99% ee) fashion is being
disclosed.
The present protocol reveals the potential of the deprotonative phospha-TMM
strategy for the synthesis of challenging five-membered carbo- and
heterocycles, especially those with spirocyclic entities and quaternary
asymmetric stereocenters. The choice of the robust chiral diamidophosphite
ligand proved to be very crucial for the desired reactivity in the
present transformation. Furthermore, the synthetic utility of the
products is demonstrated by multiple transformations such as reductions,
oxidations, and alkylations.