Regiodivergent Synthesis of Spirocyclic Compounds through Pd-Catalyzed Regio- and Enantioselective [3+2] Spiroannulation

A novel Pd-0-catalyzed highly regio- and enantioselective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. Notably, the regioselectivity could be dominated by fine-tuning of the Pd-pi-allyl intermediate. An array of coupling partners could be well-tolerated with excellent regio-, and enantioselectivities. Moreover, the potential application of this reaction was exemplified by several further transformations.

Automated summary

A novel Pd-0-catalyzed highly selective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. The regioselectivity of the reaction can be controlled by fine-tuning the Pd-pi-allyl intermediate, with excellent toleration of various coupling partners and enantioselectivities demonstrated through further transformations.