Nickel-Catalyzed Vinylidene Insertions into O-H Bonds

A (pybox)Ni catalyst (where pybox = pyridine-bis(oxazoline)) promotes the reductive cyclization of beta-hydroxy 1,1-dichloroalkenes to form 2,3-dihydrofurans. The substrates for this reaction are conveniently prepared by an aldol addition, followed by one-carbon homologation. Chiral substrates are accessible in highly enantioenriched form, allowing for the synthesis of stereochemically complex 2,3,4-trisubstituted products. Mechanistic studies support a vinylidene O-H insertion rather than a C-O cross-coupling pathway.

Automated summary

The (pybox)Ni catalyst enables the reductive cyclization of beta-hydroxy 1,1-dichloroalkenes to form 2,3-dihydrofurans, providing a convenient method for the synthesis of stereochemically complex products. Chiral substrates can be accessed in highly enantioenriched form, with mechanistic studies supporting a vinylidene O-H insertion pathway.