Why [4 + 2 + 1] but Not [2 + 2 + 1]? Why Allenes? A Mechanistic Study of the Rhodium-Catalyzed [4 + 2 + 1] Cycloaddition of Generated Ene-Ene-Allenes and Carbon Monoxide.

Transition metal-catalyzed [4 + 2 + 1] cycloaddition of generated ene/yne-ene-allenes (from ene/yne-ene propargyl esters) and carbon monoxide (CO) gives the [4 + 2 + 1] cycloadducts rather than [2 + 2 + 1] cycloadducts. Investigating the mechanism of this [4 + 2 + 1] reaction and understanding why the [2 + 2 + 1] reaction does not compete and the role of the allene moiety in the substrates are important. This is also helpful to guide the future design of new [4 + 2 + 1] cycloadditions. Reported here are the kinetic and computed studies of the [4 + 2 + 1] reactions of ene-ene propargyl esters and CO. A quantum chemical study (at the DLPNO-CCSD(T)//BMK level) revealed that the [4 + 2 + 1] reaction includes four key steps, which are 1,3-acyloxy migration (rate-determining step), oxidative cyclization, CO migratory insertion, and reductive elimination. The allene moiety in the substrates is critical for providing additional coordination to the rhodium center in the final step of the catalytic cycle, which in turn favors the reductive elimination transition state in the [4 + 2 + 1] rather than in the [2 + 2 + 1] pathway. The CO insertion step in the [4 + 2 + 1] reaction, which could occur through either the UP (favored here) or DOWN CO insertion pathway, has also been deeply scrutinized, and some guidance from this analysis has been provided to help the future design of new [4 + 2 + 1] reactions. Quantum chemical calculations have also been applied to explain why [4 + 2] and [4 + 1] cycloadditions do not happen and how trienes as side products for some substrates are generated.