Treatment of (aR)‐[1,1′binaphthalene]‐8,8′‐diol ((−)‐1) with hexamethylphosphorous triamide afforded the N,N‐dimethylphosphoramidite (−)‐3 (Scheme 1). The synthesis of the analogous N,N‐diisopropylphosphoramidite 4 failed, however, and afforded the acyclic phosphonamidate (−)‐5. The application of the cyclic phosphoramidite (−)‐3 towards asymmetric catalysis was investigated. The borane reduction of acetophenone (6) to (R)‐1‐phenylethanol (7) in the presence of (−)‐3 proceeded with 96% ee (Scheme 2). The use of (−)‐3 as ligand in several Cu‐catalyzed addition and substitution reactions resulted in enantioselectivities ranging from 0 to 50% (Schemes 3 and 4).