Isolation and enantiostability of the B-chiral bis(salicylato)borate anions [B(Sal)] and [B(Sal)]

The chiral spiroborate anions [B S (Sal) 2 ] and [B R (Sal) 2 ], ( R and S subscripts indicate boron stereochemistry) have been isolated as 1 : 1 quininium and 1 : 2 sparteinium salts, [HQuin][B S (Sal) 2 ] and [H 2 Spa][B R (Sal) 2 ] 2 respectively, by either cation metathesis or a simple one-pot synthesis involving reaction of boric and salicylic acids with the alkaloid base. Circular dichroism (CD) spectroscopy shows that the B-based chirality is stable in polar aprotic media, such as DMF or DMSO, though labile in protic solutions. Enantiopure salts with achiral counter-cations such as [NBu 4 ][B R (Sal) 2 ] may then be prepared by exchange, so these B-chiral anions may have use in metathesis-based resolutions. Due to a site disorder the anion in [H 2 Spa][B R (Sal) 2 ] 2 is limited to 70% ee, however an enantiopure analogue [H 2 Spa][B R (5-Cl-Sal) 2 ] 2 is readily formed using 5-chlorosalicylic acid. This also indicates a wide family of stable enantiopure B-chiral anions may be isolated by this approach. Both chiral hands of bis(salicylato)borate anion [B S (Sal) 2 ] and [B R (Sal) 2 ] are isolated and CD spectroscopy indicates they can be configurationally stable.