Acid-Catalyzed Benzylation Enabled by Benzyl 4-Methylpent-4-enoate.

A benzylating method enabled by acid-catalyzed hydrolactonization of benzyl 4-methylpent-4-enoate (BMP) was reported. Key advantages of the method include the structural simplicity, stability, and synthetic scalability of the reagents, mild and weakly acid catalytic conditions with excellent functional group tolerance, and high efficiency with broad applicability to various alcohols. Moreover, this method is further expanded to efficient naphthylmethylation and steroidation. The latter facilitates diversity-oriented synthesis of pseudo-steroidal glycosides.