Facile Synthesis of Enantiopure 1,1′-Spirobiindane-7,7′-diol and Its 4,4′-Derivatives: Application in Enantioselective Addition of Diethylzinc to Aromatic Aldehydes

Abstract

The enantiopure 1,1′-spirobiindane-7,7′-diol (SPINOL) and its 4,4′-derivatives 4,4′-diiodo-1,1′-spirobiindane-7,7′-diol (DISPINOL) and 4,4′-dimethyl-1,1′-spirobiindane-7,7′-diol (DMSPINOL) have been synthesized effectively via (1S)-(-)-4,4′-dibromo-1,1′-spirobiindane-7,7′-diyl bismenthyl carbonate with BuLi following the cleavage of the bismenthyl carbonate. Their absolute configurations were assigned by chemical correlation. They are also applied in the form of their Ti-alkoxides as catalysts for the addition of diethylzinc to aldehydes. The addition reactions proceeded with high conversions and enantioselectivities up to 88%. The effect of substitution of the substrate was studied.

Keywords

alkylations - aldehydes - stereoselectivity - spiro compounds - enantiomeric resolution - protecting groups

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