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1H-Isochromene derivatives are found in a variety of biologically active molecules and are therefore of interest to the pharmaceutical industry. These organic moieties have been successfully synthesized using a novel gold(I)-catalyzed cyclization. This reaction affords 1H-isochromenes in a 41% unoptimized yield from simple benzylic alcohols. This methodology has been applied to the implementation of a gold-cleavable alcohol protecting group that generates a similar 1H-isochromene as a byproduct. The cyclization regenerates the alcohol with an 80% yield.