Asymmetric Synthesis and Application of Chiral Spirosilabiindanes

Xin Chang; Pei-Long Ma; Hong-Chao Chen; Chuan-Ying Li; Peng Wang

doi:10.1002/anie.202002289

Asymmetric Synthesis and Application of Chiral Spirosilabiindanes

Angew Chem Int Ed Engl. 2020 Jun 2;59(23):8937-8940. doi: 10.1002/anie.202002289. Epub 2020 Mar 24.

Authors

Xin Chang^{1

2}, Pei-Long Ma¹, Hong-Chao Chen¹, Chuan-Ying Li², Peng Wang^{1

3}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
² Department of Chemistry, Zhejiang Sci-Tech University, Xiasha West Higher Education District, Hangzhou, 310018, P. R. China.
³ CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.

PMID: 32141185
DOI: 10.1002/anie.202002289

Abstract

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.

Keywords: asymmetric catalysis; ligand design; silanes; spirocompounds; synthetic methods.

Abstract

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