1,1’-Binaphthyl-2,2’-diol, or BINOL, has been used as chiral auxiliary for the asymmetric synthesis since 1983.
Hisashi Yamamoto first utilized (R)-BINOL as a chiral auxiliary in the asymmetric synthesis of limonene, which is an example of cyclic mono-terpenes. (R)-BINOL mononeryl ether was prepared by the monosilylation and alkylation of (R)-BINOL as the chiral auxiliary. Followed with the reduction by organoaluminum reagent, limonene was synthesized with low yields (29% yield) and moderate enantiomeric excesses up to 64% ee.
The preparation of a variety of enantiomerically pure uncommon R-amino acids can be achieved by the alkylation of chiral glycine derivatives possessing axially chiral BINOL as an auxiliary. It has been depicted by Fuji et al. Based on different electrophile, the diastereomeric excess varied from 69% to 86.
Protected at the aldehyde function with (R)-BINOL,  reacted diastereoselectively with Grignard reagents to afford protected atrolactaldehyde with moderate to excellent diastereomeric excess and high yields.
BINOL was also used as a chiral auxiliary to control the formation of a P-stereocenter in an asymmetric metal-catalyzed C-P coupling process. Mondal et al. discovered that the Pd-catalysed C-P cross-coupling reaction between axially chiral BINOL-based phosphoramidites and aryl halides or triflates proceeds with excellent stereoselectivity due to the presence of BINOL near the reacting P center.