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A new and facile method for the synthesis of 6H‐dinaphtho[c,e][1,2]oxaphosphinines starting from dinaphthol (BINOL) is described. The ring‐opening of an intermediary dinaphtho[2,1‐b;1′,2′‐d]furan proceeds with extremely high diastereoselectivity and forms the thermodynamically most stable product. The stereochemistry was elucidated by 31P NMR spectroscopy and X‐ray structural analysis. Epimerization...
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