Titanocene-Catalyzed [2+2] Cycloaddition of Bisenones and Comparison with Photoredox Catalysis and Established Methods

Cp2Ti(TFA) is a broadly applicable catalyst for the [2+2] cycloaddition of bisenones by inner-sphere electron transfer. The attractiveness of this mechanism is shown by comparison with outer-sphere ET methods. DFT calculations show that the reaction proceeds through a unique unfavorable 5-exo (the rate-determining step) and a favorable 4-exo cyclization.

Automated summary

Cp2Ti(TFA) is a versatile catalyst for the [2+2] cycloaddition of bisenones through inner-sphere electron transfer, with a unique 5-exo step as the rate-determining step followed by a favorable 4-exo cyclization.