Organocatalytic DYKAT of Si-Stereogenic Silanes
| Autor: | Hui Zhou, Roberta Properzi, Markus Leutzsch, Paola Belanzoni, Giovanni Bistoni, Nobuya Tsuji, Jung Tae Han, Chendan Zhu, Benjamin List |
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| Jazyk: | angličtina |
| Rok vydání: | 2023 |
| Předmět: |
Chiral organosilane
dynamic kinetic asymmetric transformation (DIKAT) amidodiphosphorimidate (IDPi) catalysts epimerization computational mechanism Colloid and Surface Chemistry computational mechanism epimerization Chiral organosilane General Chemistry dynamic kinetic asymmetric transformation (DIKAT) Biochemistry Catalysis amidodiphosphorimidate (IDPi) catalysts |
| Popis: | Chiral organosilanes do not exist in nature and are therefore absent from the chiral pool. As a consequence, synthetic approaches toward enantiopure silanes, stereogenic at silicon, are rather limited. While catalytic asymmetric desymmetrization reactions of symmetric organosilicon compounds have been developed, the utilization of racemic silanes in a dynamic kinetic asymmetric transformation (DYKAT) or dynamic kinetic resolution (DKR) would significantly expand the breadth of accessible Si-stereogenic compounds. We now report a DYKAT of racemic allyl silanes enabled by strong and confined imidodiphosphorimidate (IDPi) catalysts, providing access to Si-stereogenic silyl ethers. The products of this reaction are easily converted into useful enantiopure monohydrosilanes. We propose a spectroscopically and experimentally supported mechanism involving the epimerization of a catalyst-bound intermediate. |
| Databáze: | OpenAIRE |
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