Construction of a Chiral Silicon Center by Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation

Yuki Naganawa; Tomoya Namba; Mayu Kawagishi; Hisao Nishiyama

doi:10.1002/chem.201501568

Construction of a Chiral Silicon Center by Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation

Chemistry. 2015 Jun 22;21(26):9319-22. doi: 10.1002/chem.201501568. Epub 2015 May 28.

Authors

Yuki Naganawa¹, Tomoya Namba², Mayu Kawagishi², Hisao Nishiyama³

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603 (Japan). yuki.n@apchem.nagoya-u.ac.jp.
² Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603 (Japan).
³ Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603 (Japan). hnishi@apchem.nagoya-u.ac.jp.

PMID: 26017852
DOI: 10.1002/chem.201501568

Abstract

Rhodium-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes is described. The original axially chiral phenanthroline ligand (S)-BinThro (Binol-derived phenanthroline) was found to work as an effective chiral catalyst for this transformation. A chiral silicon stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five-membered organosilanes incorporating chiral silicon centers with high enantioselectivities (up to 91 % ee). The putative active Rh(I) catalyst takes the form of an N,N,O-tridentate coordination complex, as determined by several complementary experiments.

Keywords: asymmetric catalysis; desymmetrization; hydrosilylation; rhodium; silicon.