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

Zhian Li; Xinmiao Liang; Boshun Wan; Fan Wu

doi:10.1055/s-2004-831238

PAPER

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

Zhian Li, Xinmiao Liang*, Boshun Wan*, Fan Wu
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China, and , Graduate School of Chinese Academy of Sciences, Beijing, P. R. China
Fax: +86(411)84379260; e-Mail: bswan@dicp.ac.cn ;

Abstract

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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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