A convenient method for palladium‐catalyzed reductive deuteration of organic substrates using deuterated hypophosphite in D₂O

Abstract

A convenient method for the deuteration of organic substrates using deuterated hypophosphite as the deuterium source was investigated. Transfer deuteration of organic substrates, such as aromatic halides, alkenes, alkynes, epoxides, and O-benzyl derivatives, in the presence of palladium on carbon in deuterium oxide proceeded efficiently to give the corresponding deuterated products in excellent yields with high deuterium contents.

Catalytic Transfer Deuteration and Hydrodeuteration: Emerging Techniques to Selectively Transform Alkenes and Alkynes to Deuterated Alkanes

“…In 2015, Oba reported a transfer deuteration of alkenes and alkynes using deuterated hypophosphite as the deuterium source and Pd/C as the catalyst [8d] . An internal alkyne such as phenylpropiolic acid undergoes transfer deuteration in near quantitative yield under the optimal reaction conditions (Scheme 33, Eq.…”

Potassium Alkoxide/Disilane-Mediated Dehalogenative Deuteration

“…6 Guided by the same mechanism, deuterodehalogenation has been achieved by employing deuterated reductive species (Scheme 1b). [12][13][14][15][16][17] In 2014, Donald et al sought to incorporate deuterium atoms with Et 3 SiD under palladium catalysis, however, they finally discovered an attractive approach using cheaper i P-rOD-d 8 as the deuterium source. Using the combination of Pd(dba) 2 and S-Phos as the catalyst, a wide range of common (hetero)aryl halides was reduced to the corresponding deuterated compounds and the isotope labeling ratios were higher than 95% (Scheme 1b-1).…”

“…12 In 2015, Oba developed a convenient Pd/C-catalyzed reductive dehalogenation of aryl halides using D 3 PO 2 in D 2 O as the deuterium sources (Scheme 1b-2). 13 The substrate scope of this method is substantial and includes aromatic halides and alkenes, alkynes, epoxides, and O-benzyl derivatives. Thereafter, the Peruncheralathan group reported a selective deuteration of aryl halides using 1 mol% of a palladium catalyst derived from Pd(OAc) 2 and Ad 2 P n Bu.…”

Hydro/Deutero Deamination of Arylazo Sulfones under Metal- and (Photo)Catalyst-Free Conditions

“…However, these transition metal-based approaches often lack regioselectivity [8,9,12], and when using substituted iodoarenes, a dehalogenation and/or alkyl group shift under acid conditions may take place [18]. On the other hand, the Ar–X/Ar–D conversion was achieved via deuterodehalogenation of (hetero)aryl halides (mainly bromides) catalyzed by Pd-complexes [19,20,21] (Scheme 1b), mediated by the potassium methoxide/disilane system [22], by Pd-catalyzed deborylation of boronate esters in THF/D 2 O 4:1 [23] or via deamination of anilines (via in situ prepared diazonium salts) [24].…”