Enantioselective [3+2] Cycloaddition of Vinylcyclopropanes with Alkenyl N-Heteroarenes Enabled by Palladium Catalysis

Vinylcyclopropanes (VCPs) are a class of useful and versatile building blocks in organic synthesis.1 They are known to generate 1,3-dipoles with a palladium catalyst, and the intermediates can react with various dipolarophiles in [3 + 2] cycloaddition to form five-membered rings. Palladiumcatalyzed asymmetric [3 + 2] cycloaddition of VCPs with strong electron-deficient olefins, including alkylidene azlacates, para-quinone methides and azadienes, has been welldeveloped.2However, no examples of enantioselective reactions involving alkenes with weak electron-withdrawing groups have been disclosed, especially alkenyl N-heteroarenes, though N-heteroarenes are important substructures of natural products,3 pharmaceuticals,4 and agrochemicals.5 How to of asymmetric reaction remains a challenge. Since the seminal work of Grignard reagents addition to 2

Automated summary

Vinylcyclopropanes (VCPs) are versatile building blocks in organic synthesis, capable of generating 1,3-dipoles and undergoing [3 + 2] cycloaddition reactions. While asymmetric reactions between VCPs and electron-deficient olefins have been well developed, enantioselective reactions involving alkenes with weak electron-withdrawing groups, particularly alkenyl N-heteroarenes, remain unexplored.