Direct Deuteration of Acrylic and Methacrylic Acid Derivatives Catalyzed by Platinum on Carbon in Deuterium Oxide

Abstract

The platinum on carbon (Pt/C)-catalyzed deuteration of acrylic and methacrylic acid derivatives in deuterium oxide (D 2 O) efficiently proceeded to give the corresponding acrylic acid-d 3 and methacrylic acid-d 5 derivatives. The olefinic functionality, as well as the methyl group on the unsaturated functionality of the substrate, were satisfactorily deuterated via the hydrogen (H)deuterium (D) exchange reaction. The obtained deuterated compounds are useful building blocks and efficiently converted to the corresponding desired products including a polymer without the degradation of the original deuterium contents.

3D Printing to Increase the Flexibility of the Chemical Synthesis of Biologically Active Molecules: Design of On-Demand Gas Generation Reactors

“…Compared to the literature, one can easily highlight the advantages of atom-economic D-labeling through the use of C 2 D 2 . Alternative synthetic approaches to incorporate deuterium labels are based on base- or metal-catalyzed exchange reactions [ 81 , 82 , 83 , 84 , 85 , 86 ], D 2 -gas use [ 87 ], or previously labeled compounds [ 88 , 89 , 90 ]. Exchange reactions consume a significant amount of deuterated starting substrate when the desired product is mixed with a many-fold excess of a deuterated source several times [ 91 , 92 ].…”

Recent Advances in the Synthesis of Deuterium‐Labeled Compounds

“…As for the deuterium substitution position. Park et al [102] . examined the H−D exchange of various acrylic and methacrylic acid derivatives in i‐PrOH/D 2 O with Pt/C as a catalyst.…”

“…As for the deuterium substitution position. Park et al [102] examined the HÀ D exchange of various acrylic and methacrylic acid derivatives in i-PrOH/D 2 O with Pt/C as a catalyst. Regardless of the attached groups, deuterium replacement only occurred on the αand β-positions of the unsaturated carbons to form their corresponding deuterium-labeled acrylic derivatives (Figure 14).…”

“…The deuterium performance over different acrylic substrates. [102] amides. A series of common antibody-drug conjugate linker side chains with more than 99% deuterium incorporation were obtained with high yields and regioselectivity.…”

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

“…In 2018, the group applied the Pt/C catalyst system to the direct deuteration of acrylic and methacrylic acid derivatives with deuterated water . The key development was the addition of hydroquinone, which suppressed the polymerization of the acrylate and methacrylate substrates and increased the isolated yield from 10% to 70% (Figure 35).…”