Bloch, J. M.; Savelson, E.; Meng, A. Q.; Ericson, M. N.; Patel, I. U.; Dickie, D. A.; Tepe, J. J.; Harman, W. D. Tungsten-Enabled Diels–Alder Cycloaddition and Cycloreversion of Arenes and Alkynes: Divergent Synthesis of Highly Functionalized Barrelenes and Arenes. Journal of the American Chemistry 2025, 17, 30146-30153.
Abstract
The Diels–Alder reaction of benzenes remains a significant synthetic challenge, owing to their highly stabilized aromatic cores. In this work, the dearomatization agent {WTp(NO)(PMe3)} is used to promote Diels–Alder reactions of dihapto-coordinated (η2) benzenes with alkynes. The resulting η2-barrelene complexes can be oxidized to liberate intact barrelenes. Alternatively, mild pyrolysis leads to the extraction of the corresponding tungsten-acetylene complex and concomitant formation of new arenes possessing substituents originating from the acetylene dienophiles.