To demonstrate the synthetic potential of the current protocol, scale-up synthesis and several transformations were performed as illustrated in Scheme 3. The [2π + 2σ] cycloaddition of BCB 1a and benzofuran-derived oxadiene 2a could be scaled up to 2.0 mmol scale almost without loss in efficiency, furnishing the desired product 3a in 81% yield (Scheme 3a). Subsequently, several transformations of 3a were conducted (Scheme 3b). The reaction of 3a with MeMgBr produced the tertiary alcohol 7 in a high yield (83%). The carbonyl and ester group of 3a was reduced to the hydroxyl group with DIBAL-H with high efficiency (8, 90% yield). Furthermore, Hydrolysis of ester group of 3a afforded the carboxylic acid 9 in excellent yield (93%).