Palladium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration

Yosuke Sato; Chihiro Takagi; Ryo Shintani; Kyoko Nozaki

doi:10.1002/anie.201705500

Palladium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration

Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9211-9216. doi: 10.1002/anie.201705500. Epub 2017 Jul 4.

Authors

Yosuke Sato¹, Chihiro Takagi¹, Ryo Shintani^{1

2}, Kyoko Nozaki¹

Affiliations

¹ Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
² Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.

PMID: 28675611
DOI: 10.1002/anie.201705500

Abstract

A palladium-catalyzed asymmetric synthesis of silicon-stereogenic 5,10-dihydrophenazasilines was developed that proceeds via an unprecedented enantioselective 1,5-palladium migration. High enantioselectivity was achieved by employing 4,4'-bis(trimethylsilyl) (R)-Binap as the chiral ligand, and a series of mechanistic investigations were carried out to probe the catalytic cycle of this process.

Keywords: asymmetric catalysis; desymmetrization; metal migration; palladium; silicon stereocenters.

Publication types

Research Support, Non-U.S. Gov't