Solid phase synthesis of selectively deuterated arenes

Abstract

A novel access to deuterated and D(3)CO-substituted arenes has been developed using immobilized triazenes as precursors. The linker system and the deuterating cleavage methodology could be shown to be compatible with various functional groups and are therefore suitable for the synthesis of derivatives only hardly available via comparable protocols.

Monitoring Reactions on Solid Phases with Raman Spectroscopy

“…The intensity of the normalised alkyne band (2112 cm −1 ) was shown to reach its maximum value after a reaction time of 5 h. A similar procedure was used to determine the reaction time for the attachment of diazonium salts to immobilised amines to give triazene linkers . This reaction is well known as a prominent procedure for the synthesis of diverse heterocycles or the introduction of valuable functionalities into an aromatic building block . We adapted the above‐described method using alkynes to a very similar approach using nitriles, which are more suitable building blocks for the reactions, as they are cheap, commercially available reagents.…”

“…To the best of our knowledge, this reaction is herein shown for the first time on solid supports. The reaction, which was monitored by the decrease of the alkyne vibrational band (2107 cm −1 , see Table ) and the simultaneous increase of the nitrile vibrational band (2224 cm −1 , see Table ) was completed after 12 h (Scheme , Figure ) …”

“…Diazonium alts are prominent functional groups that offer unique transformations in organic chemistry, such as the Balz–Schiemann reaction, Sandmeyer reaction and the formation of triazenes. The latter have been used extensively for the introduction of functional groups and heterocycle synthesis on solid supports . To the best of our knowledge, in situ monitoring of the nascent diazonium species by Raman or IR spectroscopy has not been reported before, although it is expected to be a suitable model system for real‐time measurements by vibrational spectroscopy due to its Raman‐active N≡N bond.…”

“…well knowna saprominent procedure for the synthesis of diverse heterocycles [54][55][56] or the introduction of valuablef unctionalitiesi nto an aromatic building block. [57][58][59][60] We adapted the above-described methodu sing alkynes to av ery similar approachu sing nitriles, which are more suitable building blocks for the reactions, as they are cheap,c ommerciallya vailable reagents. It was demonstrated that the formation of the nitrile-bearing triazene 6 by coupling of 4-cyanobenzenediazonium tetrafluoroborate( 5)w ith benzylamine resin (gained from Merrifield resin 4 in one step) can be used as model system to analyse the progress of the triazene-forming reaction.…”

Organische Chemie 2011

“…Weiterhin wurde eine Domino‐Kreuzmetathese‐Hydrierung vorgestellt, bei welcher der homogene Hydrierkatalysator aus dem Grubbs‐Katalysator durch Zugabe von Et3SiH in situ entsteht 113. Durch Spaltung eines Dithioester‐Linkers (95) gelingt es, trifluormethylierte Arene herzustellen,114 Deuterolyse des Triazen‐Linkers (96) ergibt selektiv deuterierte oder D3CO‐substituierte Aromaten 115…”