Defective Ultrathin ZnIn₂S₄ for Photoreductive Deuteration of Carbonyls Using D₂O as the Deuterium Source

Abstract

Deuterium (D) labeling is of great value in organic synthesis, pharmaceutical industry, and materials science. However, the state‐of‐the‐art deuteration methods generally require noble metal catalysts, expensive deuterium sources, or harsh reaction conditions. Herein, noble metal‐free and ultrathin ZnIn2S4 (ZIS) is reported as an effective photocatalyst for visible light‐driven reductive deuteration of carbonyls to produce deuterated alcohols using heavy water (D2O) as the sole deuterium source. Defective two‐dimensional ZIS nanosheets (D‐ZIS) are prepared in a surfactant assisted bottom‐up route exhibited much enhanced performance than the pristine ZIS counterpart. A systematic study is carried out to elucidate the contributing factors and it is found that the in situ surfactant modification enabled D‐ZIS to expose more defect sites for charge carrier separation and active D‐species generation, as well as high specific surface area, all of which are beneficial for the desirable deuteration reaction. This work highlights the great potential in developing low‐cost semiconductor‐based photocatalysts for organic deuteration in D2O, circumventing expensive deuterium reagents and harsh conditions.

Radical deuteration

“…For instance, defective ultrathin ZnIn 2 S 4 displays omnipotent reductive deuteration ability for all kinds of unsaturated bonds, including CC, CO and CN. 14 A polymeric semiconductor PCN enables deuteron-methylation of amines with CD 3 OD, 49 and photodecarboxylase Cv FAP mutants realize the kinetic resolution of racemic acids and afford chiral deuterated products. 31 These achievements are still challenging in the organic catalytic field, but it is believed that interdisciplinary collaboration will lead to more possibilities for exploring new radical deuteration methods.…”

“…In 2021, Sun and co-workers 14 the protic sacrificial reagent. A range of deuterium-labelled alcohols were obtained in good yields and D-incorporation (Scheme 10).…”

“…In 2021, Sun and co-workers 14 prepared defective two-dimensional ZnIn 2 S 4 nanosheets (D-ZIS) by in situ modification of ZnIn 2 S 4 (ZIS) with the surfactant and found that the defect sites of D-ZIS are beneficial to charge carrier separation and active D-species generation. Therefore, D-ZIS performs as an effective photocatalyst for the reductive deuteration of unsaturated chemicals including aromatic/aliphatic ketones, aldehydes, alkenes and imines.…”

Photocatalytic Transfer Hydrogenation Reactions Using Water as the Proton Source

“…Shortly incorporation) under visible-light irradiation using CdSe quantum dots as the photocatalyst (Scheme 6a). 57 59 These strategies provided promising insights into the sustainable and eco-friendly organic synthesis of value-added deuterated chemicals. In addition, all of the above deuteration studies have also attempted deuteration synthesis of pharmaceutical intermediates (Figure 5), pointing to the potential of the PWDTH technique for the pharmaceutical industry.…”

“…Zhao et al realized the synthesis of deuterium-labeled alkenes with distinguished levels of D incorporation (99%) over nickel nanoparticles supported on carbon nitride (Ni/C 3 N 4 ) (Scheme b) . Also, Sun et al reported a metal-free defective ultrathin ZnIn 2 S 4 nanosheet (D-ZIS) catalyst for photocatalytic deuteration of carbonyls utilizing the in situ generated D protons from D 2 O splitting with decent deuteration incorporation ratios (Scheme c) . These strategies provided promising insights into the sustainable and eco-friendly organic synthesis of value-added deuterated chemicals.…”