Asymmetric Synthesis and Application of Chiral Spirosilabiindanes

Reported here is the development of a class of chiral spirosilabiindane scaffolds by Rh‐catalyzed asymmetric double hydrosilation, for the first time. Enantiopure SPSiOL (spirosilabiindane diol), a new type of chiral building block for the preparation of various chiral ligands and catalysts, was readily prepared on greater than 10 gram scale using this protocol. The potential of this new spirosilabiindane scaffold in asymmetric catalysis was preliminarily demonstrated by development of the corresponding monodentate phosphoramidite ligands (SPSiPhos), which were used in both a Rh‐catalyzed hydrogenation and a Pd‐catalyzed intramolecular carboamination. Designer scaffolds: Reported here is the rational design, asymmetric synthesis, and application of chiral spirosilabiindane scaffolds. Highly enantioselective synthesis of spirosilabiindanes is demonstrated for the first time by using a Rh‐catalyzed double hydrosilation. The versatility of this new chiral scaffold was demonstrated by the gram‐scale synthesis of SPSiOL, and application of its phosphoramidite derivatives as ligands in asymmetric catalysis.