Formation of carbenoid intermediates in the reaction of ditertiobutyl ketone with low-valent titanium reagents

Treatment of tBu2CO with TiCl4 and Li(Hg) in THF gave the hydrocarbon tBu2CH2 as the major product (40% yield); 60% of the total quantity of tBu2CH2 was liberated after hydrolysis of the reaction mixture. Similar experiments with THF-d8 and D2O afforded tBu2CHD and tBu2CD2, indicating that carbenoid species tBu2C[Ti] are likely intermediates in the reaction of tBu2CO with low-valent titanium reagents.