B(C6F5)3-Catalyzed Sequential Additions of Terminal Alkynes to para-Substituted Phenols: Selective Construction of Congested Phenol-Substituted Quaternary Carbons

We have developed a borane-catalyzed sequential addition of terminal alkynes to para-substituted phenols, which affords a wide range of ortho-propargylic alkylated phenols bearing congested quaternary carbons. Control experiments combined with DFT calculations suggest that the reaction undergoes a sequential phenol alkenylation/hydroalkynylation process. Further extension of this strategy to the construction of triaryl-substituted quaternary carbons demonstrates the broad utility of this method.

Automated summary

A borane-catalyzed sequential addition of terminal alkynes to para-substituted phenols has been developed, yielding ortho-propargylic alkylated phenols with congested quaternary carbons. Control experiments and DFT calculations suggest a sequential phenol alkenylation/hydroalkynylation process. The extension of this strategy to the construction of triaryl-substituted quaternary carbons demonstrates the broad utility of this method.