Ruthenium(II)biscarboxylate‐Catalyzed Hydrogen‐Isotope Exchange by Alkene C−H Activation

Abstract

Ruthenium(II) biscarboxylate catalysis enabled efficient hydrogen isotope exchange of acrylic C−H bonds with user‐friendly D2O. The C−H labelling was characterized by excellent positional selectivity and a broad functional group tolerance. The deuteration was successfully conducted on 55 mmol scale with TONs of >1000, while mechanistic studies provided insights into ruthenium(II) oxidase catalysis. The obtained deuterated alkenes enabled the synthesis of labeled standards for mass spectrometry of irradiated foodstuffs.

Highlights of C (sp2)–H hydrogen isotope exchange reactions

“…In a recent publication by Bechtoldt and Ackermann on the kinetics of ruthenium‐catalysed C–H activation, incorporation of deuterium into alkenes was observed . Ruthenium (II) biscarboxylates, prepared from cymene ruthenium (II) chloride dimer (Figure ), were observed to incorporate deuterium into a series of acrylates using D 2 O or CH 3 OD as the deuterium source.…”

Platinum on carbon-catalysed site-selective H–D exchange reaction of allylic alcohols using alkyl amines as a hydrogen source

“…Several research groups have reported the H–D exchange reaction of alkenes using homogeneous transition metal catalysts (iridium, ruthenium, or rhodium) with a deuterium source (benzene- d 6 , acetic acid- d 4 , methanol- d 4 , or D 2 O). 11 However, these methods require expensive homogeneous metal catalysts, which sometimes leads to metal residues contaminating the product after the reaction. Therefore, the development of a practical and efficient H–D exchange of alkene derivatives using a heterogeneous metal catalyst is desired.…”

A Protocol for the Ortho-Deuteration of Acidic Aromatic Compounds in D2O Catalyzed by Cationic RhIII

“…We considered that this method should also be viable for vinylic acids and began studying the reaction on cinnamic acids. Notably, Ru II catalysts are known for promoting HDE on vinylic acids in the presence of either CD 3 OD or D 2 O . Simple cinnamic acid showed almost complete deuteration at the β-carbon (Scheme , 2a ).…”