Chiral Chalcogenyl-Substituted Naphthyl- and Acenaphthyl-Silanes and Their Cations

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Jul 7

PMID 32627900

Citations 3

Authors

Sandra Kunzler

Saskia Rathjen

Katherina Ruger

Marie S Wurdemann

Marcel Wernke

Patrik Tholen

Corinna Girschik

Marc Schmidtmann

Yannick Landais

Thomas Muller

Affiliations

Soon will be listed here.

Abstract

Cyclic silylated chalconium borates 13[B(C F ) ] and 14[B(C F ) ] with peri-acenaphthyl and peri-naphthyl skeletons were synthesized from unsymmetrically substituted silanes 3, 4, 6, 7, 9 and 10 using the standard Corey protocol (Chalcogen Ch=O, S, Se, Te). The configuration at the chalcogen atom is trigonal pyramidal for Ch=S, Se, Te, leading to the formation of cis- and trans-isomers in the case of phenylmethylsilyl cations. With the bulkier tert-butyl group at silicon, the configuration at the chalcogen atoms is predetermined to give almost exclusively the trans-configurated cyclic silylchalconium ions. The barriers for the inversion of the configuration at the sulfur atoms of sulfonium ions 13 c and 14 a are substantial (72-74 kJ mol ) as shown by variable temperature NMR spectroscopy. The neighboring group effect of the thiophenyl substituent is sufficiently strong to preserve chiral information at the silicon atom at low temperatures.

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Chiral Chalcogenyl-Substituted Naphthyl- and Acenaphthyl-Silanes and Their Cations.

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PMID: 32627900 PMC: 7756486. DOI: 10.1002/chem.202002977.

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