Synthesis of Novel BINOL Analogs: 3,3′‐Dicarbonyl‐1,1′‐binaphthyl‐4,4′‐diols as Precursors to the Uncharted 5,5′‐Binaphtho[2,1‐d]isoxazole

[1,1′‐Binaphthalene]‐2,2′‐diol (BINOL) analog, [1,1′‐binaphthalene]‐4,4′‐diol, obtained by direct oxidative coupling of 1‐naphthol, is acylated to [1,1′‐binaphthalene]‐4,4′‐diyl diacetate and then rearranged by the Fries reaction to 1,1 ' ‐{4,4 ' ‐dihydroxy‐[1,1 ' ‐binaphthalene]‐3,3 ' ‐diyl}bis(ethan‐1‐one). Incorporation of aldehyde groups at the 3,3 ' positions of [1,1′‐binaphthalene]‐4,4′‐diol required oxidative coupling of 1‐methoxynaphthalene to 4,4′‐dimethoxy‐1,1′‐binaphthalene, bromination, formylation, and demethylation. Incorporation of benzoyl groups at the 3,3 ' positions of [1,1′‐binaphthalene]‐4,4′‐diol required subjecting either 1‐(4‐bromo‐1‐hydroxy‐2‐naphthyl)(phenyl)methanone to the Ullmann reaction conditions or 4,4′‐dimethoxy‐1,1′‐binaphthalene to the Friedel–Crafts reaction with benzoyl chloride. The 1,1′‐(4,4′‐dihydroxy‐1,1′‐binaphthalene‐3,3′‐diyl)dicarbonyls are converted to the corresponding dioximes, which then underwent cyclodehydration to the respective novel 5,5 ' ‐binaphtho[2,1‐ d ]isoxazoles.