In recent years, visible light-driven organic photochemical synthesis has attracted wide research interest from academic and industrial communities due to its features of green and sustainable chemistry. In this flourishing area, Chinese chemists have devoted great efforts to different aspects of synthetic chemistry. This review will summarize their representative work according to the following categories: C–H functionalization, synthesis of aromatic aza-heterocycles, asymmetric organic photochemical synthesis, transformations of small molecules and biomolecule-compatible reactions.

Visible light-driven organic photochemical synthesis in China

ConspectusCross-coupling reactions have been established as potential tools for manufacture of complex molecular frameworks of diversified interests by connecting two simple molecules through the formation of a carbon–carbon (C–C) or a carbon–heteroatom (C–X) bond. Conventional cross-couplings are transition metal-catalyzed reactions between electrophiles and nucleophiles. Generally, the electrophilic partner is an aryl or alkenyl halide, the nucleophile is an organometallic reagent, and both are obtained from prefunctionalization of their corresponding hydrocarbons. During the past decade, transition metal-catalyzed dehydrogenative cross-couplings between two carbon–hydrogen (C–H) bonds and between one C–H bond and one heteroatom–hydrogen (X–H) bond, which build a C–C and a C–X linkage respectively, have emerged as an attractive strategy in synthetic chemistry. Such straightforward couplings allow use of less functionalized reagents, thus reducing the number of steps to the target molecule and minimizing...

Photocatalytic Activation of Less Reactive Bonds and Their Functionalization via Hydrogen-Evolution Cross-Couplings.

The late stage functionalization (LSF) of complex biorelevant compounds is a powerful tool to speed up the identification of structure-activity relationships (SARs) and to optimize ADME profiles. To this end, visible-light photocatalysis offers unique opportunities to achieve smooth and clean functionalization of drugs by unlocking site-specific reactivities under generally mild reaction conditions. This review offers a critical assessment of current literature, pointing out the recent developments in the field while emphasizing the expected future progress and potential applications. Along with paragraphs discussing the visible-light photocatalytic synthetic protocols so far available for LSF of drugs and drug candidates, useful and readily accessible synoptic tables of such transformations, divided by functional groups, will be provided, thus enabling a useful, fast, and easy reference to them.

Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds.

Visible-light initiated aerobic oxidations: a critical review

Direct activation of H-phosphine oxide to react with an unsaturated carbon–carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in b...

Cobaloxime Catalysis: Selective Synthesis of Alkenylphosphine Oxides under Visible Light.

Visible Light Promoted Synthesis of Indoles by Single Photosensitizer under Aerobic Conditions

As one of the most ubiquitous bulk reagents available, the intrinsic chemical inertness of tetrahydrofuran (THF) makes direct and site-selective C(sp 3 )-H bond activation difficult, especially under redox neutral condition. Here, we demonstrate that semiconductor quantum dots (QDs) can activate α-C-H bond of THF via forming QDs/THF conjugates. Under visible light irradiation, the resultant alkoxyalkyl radical directly engages in radical cross-coupling with α-amino radical from amino C-H bonds or radical addition with alkene or phenylacetylene, respectively. In contrast to stoichiometric oxidant or hydrogen atom transfer reagents required in previous studies, the scalable benchtop approach can execute α-C-H bond functionalization of THF only by a QD photocatalyst under redox-neutral condition, thus providing a broad of value added chemicals starting from bulk THFs reagent. The high step- and atom-economy, high efficiency and broad substrate scope make the photocatalysis with QDs and visible light promising in both academic and industrial setting.

Direct, Site-Selective and Redox-Neutral α-C−H Bond Functionalization of Tetrahydrofurans via Quantum Dots Photocatalysis

Photoredox Oxo-C(sp3)-H Bond Functionalization via in Situ Cu(I)-Acetylide Catalysis.

Direct C(sp)-H/Si-H Cross-Coupling via Copper Salts Photocatalysis.

Metal–organic frameworks (MOF) have been studied extensively for the adsorption and catalytic conversion of CO2. However, previous studies mainly focused on the adsorption capabilities of partially or totally Ce substituted UiO-66, there are few studies focusing on transformation of the structure and catalytic activity of these materials. In this work, a series of Zr/Ce-based MOFs with UiO-66 architecture catalysts were prepared for the conversion of CO2 into value-added dimethyl carbonate (DMC). Owing to the different addition order of the two metals, significantly varied shapes and sizes were observed. Accordingly, the catalytic activity is greatly varied by adding a second metal. The different catalytic activities may arise from the different acid–base properties after Ce doping as well as the morphology and shape changes. Besides, the formation of terminal methoxy (t-OCH3) was found to be the rate limiting step. Finally, the reaction mechanism of CO2 transformation in the presence of a dehydrating agent was proposed.

https://pubs.rsc.org/en/content/articlepdf/2022/ra/d2ra02680e

Zi-Qi Song

Papers

Visible Light Promoted Synthesis of Indoles by Single Photosensitizer under Aerobic Conditions

Direct, Site-Selective and Redox-Neutral α-C−H Bond Functionalization of Tetrahydrofurans via Quantum Dots Photocatalysis

Photoredox Oxo-C(sp3)-H Bond Functionalization via in Situ Cu(I)-Acetylide Catalysis.

Direct C(sp)-H/Si-H Cross-Coupling via Copper Salts Photocatalysis.

Enhanced transformation of CO2 over microporous Ce-doped Zr metal–organic frameworks