Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones

Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caus...

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Bibliographic Details
Published in:Communications chemistry 2023-11, Vol.6 (1), p.255-255, Article 255
Main Authors: Conen, Peter, Nickisch, Roman, Meier, Michael A. R.
Format: Article
Language:English
Subjects:
639/638/224/685
639/638/403/933
639/638/403/934
639/638/549/933
639/638/77/889
Additives
Alkenes
Alkylidene
Chemical synthesis
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Cross coupling
Electrochemical analysis
Emission
Optical measuring instruments
Optical properties
Organometallic compounds
Potassium carbonate
Reagents
Substitutes
Substrates
Sulfur
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Summary:Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caused by the sterically congested double bond. Herein, we present an efficient and metal-free procedure for the synthesis of tetraarylethylenes via alkylidene-homocoupling of N -tosylhydrazones, derived from readily available benzophenones, in excellent yields. The method relies only on cheap and benign additives, i.e . elemental sulfur and potassium carbonate, and easily competes with other established procedures in terms of scope, yield and practicability. A mechanistic study revealed a diazo compound, a thioketone and a thiirane as key intermediates in the pathway of the reaction. Based on this, a modified method, which allows for selective alkylidene-cross-coupling, generating a broader scope of tri- and tetrasubstituted olefins in good yields, is showcased as well. Tetraphenylethylenes (TPEs) are known for their aggregation-induced emission and electrochemical properties of value for optical sensors, however, established synthetic routes suffer from several limitations. Here, the authors develop a metal-free route to TPEs and other alkenes via a sulfur-mediated coupling of N -tosylhydrazones, achieving good yields and a broad substrate scope.
ISSN:2399-3669
2399-3669
DOI:10.1038/s42004-023-01058-2