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Publication . Article . 2022

Catalytic Stereoconvergent Synthesis of Homochiral β-CF 3 , β-SCF 3 , and β-OCF 3 Benzylic Alcohols

Andrej Emanuel Cotman; Pavel A. Dub; Maša Sterle; Matic Lozinšek; Jaka Dernovšek; Živa Zajec; Anamarija Zega; +2 Authors
Open Access
English
Published: 13 Oct 2022
Publisher: HAL CCSD
Abstract

International audience; We describe an efficient catalytic strategy for enantio- and diastereoselective synthesis of homochiral β-CF3, β-SCF3, and β-OCF3 benzylic alcohols. The approach is based on dynamic kinetic resolution (DKR) with Noyori–Ikariya asymmetric transfer hydrogenation leading to simultaneous construction of two contiguous stereogenic centers with up to 99.9% ee, up to 99.9:0.1 dr, and up to 99% isolated yield. The origin of the stereoselectivity and racemization mechanism of DKR is rationalized by density functional theory calculations. Applicability of the previously inaccessible chiral fluorinated alcohols obtained by this method in two directions is further demonstrated: As building blocks for pharmaceuticals, illustrated by the synthesis of heat shock protein 90 inhibitor with in vitro anticancer activity, and in particular, needle-shaped crystals of representative stereopure products that exhibit either elastic or plastic flexibility, which opens the door to functional materials based on mechanically responsive chiral molecular crystals.

Subjects by Vocabulary

Universal Decimal Classification: udc:54

Subjects

[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, adaptive crystals, asymmetric catalysis, density functional calculations, drug design, fluorine, hydrogenation, kinetic resolution, ruthenium, alcohols, catalysts, crystals, ketones, stereoselectivity, Literature and Literary Theory, History, Cultural Studies

Funded by
EC| HiPeR-F
Project
HiPeR-F
Challenging the Oxidation-State Limitations of the Periodic Table via High-Pressure Fluorine Chemistry
  • Funder: European Commission (EC)
  • Project Code: 950625
  • Funding stream: H2020 | ERC | ERC-STG
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